JP2001312022A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion having long shelf life, high sensitivity and high contrast. SOLUTION: In the silver halide photographic emulsion containing silver halide grains having the spectral absorption maximum wavelength at <500 nm and a light absorption strength of >=60 or the spectral absorption maximum wavelength at >=500 nm and a light absorption intensity of >=100, the coefficient of variation in the intergrain distribution of light absorption strength is <=100%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic material using a spectrally sensitized silver halide photographic emulsion.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials. In a silver halide photographic emulsion, the sensitizing dye adsorbed on the surface of the silver halide grains absorbs light incident on the photographic material and transmits the light energy to the silver halide grains to obtain photosensitivity. Therefore, in the spectral sensitization of silver halide, the light energy transmitted to the silver halide can be increased by increasing the light absorptivity per unit grain surface area of the silver halide grains, thereby increasing the spectral sensitivity. It is believed that sensitivity is achieved. In order to improve the light absorptance on the surface of the silver halide grains, the amount of the spectral sensitizing dye adsorbed per unit grain surface area may be increased. However, the amount of sensitizing dye adsorbed on the surface of silver halide grains is limited, and it is difficult to adsorb more dye chromophore than single-layer saturated adsorption (that is, one-layer adsorption). Therefore,
At present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is still low.

A method proposed to solve these points is described below. PB Gilman, Jr., et al., Photographic Science and Engine Nearing (Photographic Science and and).
In Engineering, Vol. 20, No. 3, 97th Contribution (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GB Bird et al., In U.S. Pat. No. 3,622,316, incorporated multiple dyes onto silver halide in multiple
sensitized by the contribution of the (ster) type excitation energy transfer.

[0004] Sugimoto et al., JP-A-63-138,341.
Nos. 64-84 and 244, spectral sensitization was performed by energy transfer from the luminescent dye. R. Steiger et al., Photographic Science and Engine Nearing (Photographic Science and)
Engineering, Vol. 27, No. 2, No. 59 (1983), an attempt was made to spectrally sensitize a gelatin-substituted cyanine dye by energy transfer. Conducted spectral sensitization by energy transfer from a cyclodextrin-substituted dye in JP-A-61-251842. Also, Richard Parton et al., European Patent 0985964A1, European Patent 0985965A1, European Patent 0985966A1, European Patent 0988565A.
In No. 1, multilayer adsorption was carried out using a combination of a cationic dye and an anionic dye, and an attempt was made to increase the sensitivity by transferring energy from the second-layer dye to the first-layer dye.

However, in these methods, the degree to which the sensitizing dye is adsorbed in multiple layers on the surface of silver halide grains is actually insufficient, and the effect of improving the sensitivity is extremely small. For this reason, it has been demanded that the interaction between the dye molecules is strengthened to realize substantially effective multilayer adsorption.

[0006] On the other hand, it has become clear that when the interaction between dye molecules is strengthened in order to realize multilayer adsorption, the distribution of dye adsorption between particles tends to be non-uniform. It has been found that the distribution of dye adsorption between particles tends to be uniform as the amount of sensitizing dye adsorbed increases in ordinary single-layer adsorption. Was an unexpected phenomenon. As a result of the analysis, there are basically two interactions for constructing the multilayer adsorption structure: (a) the interaction between the first and second dye molecules and (b) the interaction between the second dye molecules. However, it was found that the distribution of the dye adsorption amount between the particles increased as the ratio of the interaction between the dye molecules in the second layer (b) increased. It was also found that not only the distribution of the dye adsorption amount between the particles, but also the distribution between the particles having the maximum absorption wavelength and the distribution between the particles having the half width of absorption were similarly nonuniform. Since it has been found that the distribution between particles in the dye-adsorbed state has an adverse effect on sensitivity and gradation, development of a technique for uniformizing particles in the dye-adsorbed state has been required.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having good storage stability, high sensitivity and high contrast, and a photographic material using the same.

[0008]

Means for Solving the Problems (1) Silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more are contained. In a silver halide photographic emulsion, the coefficient of variation of the distribution of light absorption between grains is 100.
% Or less. (2) Halogenated with a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more. In a silver halide photographic emulsion containing silver grains, when the maximum value of the spectral absorptance by the sensitizing dye is Amax, the variation in intergranular distribution of the wavelength interval of the shortest wavelength and the longest wavelength showing 50% of Amax A silver halide photographic emulsion characterized by a coefficient of 50% or less (3) a light absorption intensity of 60 or more with a maximum spectral absorption wavelength of less than 500 nm or a light absorption intensity of 100 or more with a maximum spectral absorption wavelength of 500 nm or more In a silver halide photographic emulsion containing silver halide grains of 50% of the total projected area
A silver halide emulsion, wherein the spectral absorption maximum wavelength of the above grains is in the range of 10 nm or less. For example, the spectral absorption maximum wavelength of 50% or more (area) of all silver halide grains in the emulsion is within ± 5 nm of the average spectral absorption maximum wavelength of all silver halide grains. Means (4) The silver halide photograph described in (1), (2) or (3), which comprises a silver halide photographic emulsion in which a sensitizing dye is adsorbed in multiple layers on the surface of silver halide grains. emulsion. (5) In the silver halide photographic emulsion described in (4),
The silver halide photographic emulsion according to (4), wherein the interaction energy between the first-layer dye and the second-layer dye is 10% or more of the total adsorption energy of the second-layer dye. (6) In the silver halide photographic emulsion described in (1) to (5), the maximum value of the spectral absorption of the emulsion by a sensitizing dye is defined as
The silver halide photographic emulsion according to any one of (1) to (5), wherein the wavelength interval between the shortest wavelength and the longest wavelength, which indicates 50% of Amax when Amax is 120 nm or less. (7) In the silver halide photographic emulsion described in (1) to (5), the maximum value of the spectral sensitivity of the emulsion by the sensitizing dye is defined as Sm.
The silver halide photographic emulsion according to any one of (1) to (5), wherein the wavelength interval between the shortest wavelength and the longest wavelength indicating 50% of Smax when ax is 120 nm or less. (8) In the silver halide photographic emulsion described in (6) or (7), the longest wavelength having a spectral absorption of 50% of Amax is from 460 nm to 510 nm, or from 560 nm to 6 nm.
The silver halide photographic emulsion according to (6) or (7), wherein the emulsion has a thickness of 10 nm or a range of 640 nm to 730 nm. (9) In the silver halide photographic emulsion described in (6) or (7), the longest wavelength showing a spectral sensitivity of 50% of Smax is from 460 nm to 510 nm, or from 560 nm to 61.
The silver halide photographic emulsion according to (6) or (7), wherein the emulsion has a thickness of 0 nm or a range of 640 nm to 730 nm. (10) The silver halide photographic emulsion contains a dye having at least one aromatic group.
The silver halide photographic emulsion according to any of (9). (11) The silver halide photographic emulsion according to any one of (1) to (10), further comprising a sensitizing dye having a basic nucleus fused with three or more rings. (12) The silver halide photographic emulsion according to (1) to (11), wherein tabular grains having an aspect ratio of 2 or more exist in an amount of 50% (area) or more of all silver halide grains in the emulsion. The silver halide photographic emulsion according to any one of (1) to (11), which is characterized in that: (13) The silver halide photographic emulsion described in (1) to (12) is selenium-sensitized.
The silver halide photographic emulsion according to any one of (12) and (13). (14) The silver halide photographic emulsion according to any one of (1) to (13), wherein the silver halide photographic emulsion described in (1) to (13) contains a silver halide-adsorbing compound other than a sensitizing dye. A silver halide photographic emulsion as described above. (15) In the silver halide grains of the silver halide photographic emulsion described in (1) to (14), the excitation energy of the second-layer dye is transferred to the first-layer dye at an efficiency of 10% or more. The silver halide photographic emulsion according to any one of (1) to (14). (16) The silver halide grains of the silver halide photographic emulsion described in (1) to (15), wherein both the first-layer dye and the second-layer dye exhibit J-band absorption.
The silver halide photographic emulsion according to any one of (1) to (15). (17) A silver halide photographic light-sensitive material comprising at least one layer of the silver halide photographic emulsion according to (1) to (16).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a silver halide photographic material using silver halide grains sensitized by a dye, comprising a silver halide photographic emulsion in which a sensitizing dye is adsorbed in multiple layers and the amount of dye adsorbed between grains is uniform. High-sensitivity silver halide photographic light-sensitive material.

In the present invention, the light absorption intensity is a light absorption area intensity by a sensitizing dye per unit particle surface area,
The optical density Log when the amount of light incident on the unit surface area of the particles is I ₀ and the amount of light absorbed by the sensitizing dye on the surface is I.
(I ₀ / (I ₀ −I)) is defined as a value integrated with respect to the wave number (cm ⁻¹ ). Integration range from 5000 cm ^-1 to 35
Up to 000 cm ^-1 .

The silver halide photographic emulsion according to the present invention has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 50 for grains having a spectral absorption maximum wavelength exceeding 500 nm.
In the case of grains having a size of 0 nm or less, silver halide grains having a light absorption intensity of 60 or more are を of the total projected area of the silver halide grains.
It is preferable to include the above. In addition, the spectral absorption maximum wavelength is 5
In the case of particles exceeding 00 nm, the light absorption intensity is preferably 150 or more, more preferably 170 or more, particularly preferably 200 or more, and the spectral absorption maximum wavelength is 50 or more.
In the case of particles having a size of 0 nm or less, the light absorption intensity is preferably 90 or more, more preferably 100 or more, and particularly preferably 120 or more. There is no particular upper limit, but preferably 2
000 or less, more preferably 1000 or less, particularly preferably 500 or less. In addition, the spectral absorption maximum wavelength is 50
For particles below 0 nm, the spectral absorption maximum wavelength is 35
It is preferably 0 nm or more.

As an example of a method for measuring the light absorption intensity,
Can use a microspectrophotometer.
You. Microspectrophotometer measures the absorption spectrum of a small area
Device that can measure the transmission spectrum of a single particle.
Noh. Of the absorption spectrum of one particle by microspectroscopy
For the measurement, see Yamashita et al.'S report (The Photographic Society of Japan, 199
6th Annual Meeting Abstracts, p. 15)
Can be. From this absorption spectrum, the absorption per particle
Although light intensity is required, the light passing through the particles is
Absorbed on two sides of the surface
Absorption intensity per particle obtained by the method described above.
It can be obtained as の of the yield strength. At this time,
The interval for integrating the absorption spectrum is
5000cm ^-1From 35000cm^-1But on the experiment
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
It may be the integral of the section including the degree. Also, the light absorption intensity increases.
The strength of the dye and the number of adsorbed molecules per unit area
These values are determined uniquely, and the oscillator strength and color of the sensitizing dye
Converted to light absorption intensity by calculating the amount of element adsorbed and particle surface area
You can do it. The oscillator strength of the sensitizing dye is
Solution area intensity (optical density x cm^-1Value proportional to
Can be obtained experimentally as
The absorption area intensity of the dye is A (optical density × cm^-1), Sensitizing color
B (mol / mol Ag) and particle surface area
C (m^Two / MolAg), the light absorption is given by the following equation:
The strength can be determined within an error range of about 10%. 0.156 × A × B / C Even if the light absorption intensity is calculated from this equation, it is based on the above-mentioned definition.
The light absorption intensity (Log (I₀ / (I₀ −
I))) is the wave number (cm^-1) And real)
The same value is obtained.

Methods for increasing the light absorption intensity include a method of adsorbing more dye chromophore on the particle surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the dye occupied area. Any of these methods may be used, but is preferably a method in which the dye chromophore is further adsorbed on the particle surface. Here, the state in which the dye chromophore is more adsorbed on the grain surface means that more bound dye is present in the vicinity of the silver halide grains, and includes the dye present in the dispersion medium. Absent. Even when the dye chromophore is covalently linked to the substance adsorbed on the particle surface, the effect of increasing the light absorption intensity is long when the linking group is long and the dye chromophore is present in the dispersion medium. It is not considered small and more adsorption. Further, in the so-called multilayer adsorption, in which the dye chromophore is adsorbed on the particle surface more than one layer, it is necessary that spectral sensitization is caused by the dye not directly adsorbed on the particle surface,
For this purpose, it is necessary to transfer excitation energy from a dye not directly adsorbed to silver halide to a dye directly adsorbed to grains. Therefore, the transfer of the excitation energy is 10
If it is necessary to take place beyond the steps, the transmission efficiency of the final excitation energy is undesirably low. One example is a case where most of the dye chromophore is present in a dispersion medium, such as a polymer dye as disclosed in JP-A-2-113239, and transmission of excitation energy is required in 10 or more steps. In the present invention, the number of coloring steps per molecule is from 1 to 3
Is preferable, and 1 to 2 are more preferable.

The chromophore described herein means an atomic group that is the main cause of the absorption band of molecules described in the Dictionary of Physical and Chemical Sciences (4th edition, Iwanami Shoten, 1987), pp.985-986. Any atomic group is possible, such as an atomic group having an unsaturated bond such as C = C and N = N.

For example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium Dye, croconium dye,
Azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye,
Fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye,
Examples include quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes. Preferably, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squarium dye, Croconium dye,
And polymethine chromophores such as azamethine dyes.
More preferably, a cyanine dye, a merocyanine dye, or 3
Nuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine Soybeans and Related Compounds".
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons, Inc.- New York, London, 1964, DM Sturmer (DMStu
rmer), Heterocyclic Compounds-Special topics in heterocyclic Chemistry
terocyclic chemistry) ", Chapter 18, Section 14, Section 4
82-515. Preferred general formulas of the dyes include general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
7, 236, pp. 30-34. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21 to 22, (XI), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or more). Below)).

The adsorption of the dye chromophore to the silver halide grains is preferably at least 1.5 layers, more preferably 1.7 layers.
More than two layers, particularly preferably two or more layers. Although there is no particular upper limit, the number is preferably 10 or less, more preferably 5 or less.

In the present invention, the state in which the chromophore is further adsorbed on the surface of the silver halide grain is defined as the sensitizing dye added to the emulsion, the dye having the smallest area occupied by the dye on the surface of the silver halide grain. The reached saturated adsorption amount per unit surface area is defined as a more saturated coating amount, and the state in which the amount of adsorption of the dye chromophore per unit area is larger than the one more saturated coating amount. The number of adsorbed layers means the amount of adsorption based on the amount of one-layer saturated coating. Here, in the case of a dye in which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in a non-linked state can be used as a reference.
The dye occupied area can be determined from an adsorption isotherm showing the relationship between the concentration of free dye and the amount of adsorbed dye, and the particle surface area. Adsorption isotherms are described, for example, by A. Hertz.
z) et al.'s Adsorption from Aqua Aquas solution
eous Solution) Advances Inn
Chemistry Series (Advances in C
Chemistry Series) No. 17,173
Page (1968) and the like.

The amount of the sensitizing dye adsorbed on the emulsion grains was determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion grains and the supernatant aqueous gelatin solution, and measuring the unadsorbed dye concentration by measuring the spectral absorption of the supernatant. Subtracting from the amount of dye added to determine the amount of adsorbed dye, and drying the precipitated emulsion particles, dissolving a certain weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and performing spectral absorption measurement Can be used to determine the amount of adsorbed dye. When a plurality of types of sensitizing dyes are used, the adsorption amount of each dye can be determined by a technique such as high performance liquid chromatography. A method for determining the amount of dye adsorbed by quantifying the amount of dye in the supernatant is described in, for example, Journal of Physical Chemistry (W. West) et al.
Physical Chemistry) Vol. 56, 1
054 (1952). However, under conditions where the amount of dye added is large, even unadsorbed dye may precipitate, and the method of quantifying the dye concentration in the supernatant may not always obtain the correct amount of dye. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide particles, the emulsion particles have an overwhelmingly high sedimentation speed, so that the particles can be easily separated from the sedimented dye, and the dye adsorbed on the particles can be easily separated. Only the quantity can be measured accurately. This method is the most reliable as a method for obtaining the dye adsorption amount. The amount of the photographically useful compound adsorbed on the particles can be measured in the same manner as the sensitizing dye. However, since the absorption is small in the visible light region, a quantitative method by high performance liquid chromatography is preferable to a quantitative method by spectral absorption.

As an example of a method for measuring the surface area of a silver halide grain, there is a method in which a transmission electron micrograph is taken by a replica method and the shape and size of each grain are obtained and calculated. In this case, the thickness of the tabular grains is calculated from the length of the shadow of the replica. As a method for taking a transmission electron microscope photograph, for example, “Electron Microscope Sample Techniques” edited by Kanto Chapter of the Electron Microscope Society of Japan, Seibodo Shinkosha 19
70th edition, Butterworth (Butterworth)
s), London, 1965, PB Hirsch et al., Electron Microscope of Chin Crystal (Electron).
Microscopy of ThinCrysta
ls).

Other methods include, for example, the journal of AM Kragin et al.
Of Photographic Science (The Jo
urnal of Photographic Sci
ence, Vol. 14, p. 185 (1966), Transactions of the Fara of JF Paddy's Transactions of the Faraday
day Society, Vol. 60, page 1325 (1
964), S. Boyer et al., Journal de Chimie Ph.
ysique et de Physicochimi
e biologice, Vol. 63, p. 1123 (1963), W. Wes
t) et al. of Journal of Physical Chemistry
Istry) Volume 56, 1054 pages (1952)
), H. Sauvenier
r) Editing, E. Klein et al. International Colloquium (International)
al Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)) can be referred to. The dye occupation area can be determined experimentally for each case by the above method, but the molecular occupation area of a commonly used sensitizing dye is approximately 80%.
Since in the vicinity Å ^2, simply all of the dye can also be estimated roughly the number of adsorption layers a dye occupation area as 80 Å ² for.

In the present invention, when the dye chromophore is adsorbed on the silver halide grains in multiple layers, the so-called first-layer dye chromophore directly adsorbed on the silver halide grains and the dye chromophore of the second or more layers The reduction potential of the group, and the oxidation potential may be any, but the reduction potential of the dye chromophore of the first layer is less than the value obtained by subtracting 0.2 v from the reduction potential of the dye chromophore of the second layer or more. It is preferably noble.

Although various methods can be used for measuring the reduction potential and the oxidation potential, the measurement is preferably carried out by phase discrimination type second harmonic AC polarography, and accurate values can be obtained. . The method for measuring the potential by the phase discrimination type second harmonic AC polarography is described in Journal of Imaging Science (Journ).
al of Imaging Science), 3rd
0, page 27 (1986).

The dye chromophore of the second or higher layer is preferably a luminescent dye. As the kind of the luminescent dye, those having a skeleton structure of a dye used for a dye laser are preferable. These are described, for example, in Mitsuo Maeda, Laser Research, 8, 694, 803, 958 (1980) and 9, 85, (1981), and F. Sehaefer.
Author, "Dye Lasers", Springer (1973).

Further, it is preferable that the maximum absorption wavelength of the first-layer dye chromophore in the silver halide photographic light-sensitive material is longer than the maximum absorption wavelength of the second or higher-layer dye chromophore. Further, it is preferable that the emission of the dye chromophore of the second layer or more overlaps with the absorption of the dye chromophore of the first layer. Also,
The first-layer dye chromophore preferably forms a J-aggregate. Further, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophore of the second layer or more also forms a J-aggregate. The energy transfer efficiency of the excitation energy of the second-layer dye to the first-layer dye is preferably 30% or more, more preferably 60%, and particularly preferably 90% or more. The efficiency of energy transfer from the second-layer dye to the first-layer dye can be determined as spectral sensitization efficiency when the second-layer dye is excited / spectral sensitization efficiency when the first-layer dye is excited.

The meanings of the terms used in the present invention are described below. Dye occupied area: occupied area per dye molecule. It can be determined experimentally from the adsorption isotherm. In the case of a dye to which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in an unlinked state is used as a reference. 80 for simplicity
A ^2. Saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of one-saturated coating. Reciprocal of the smallest dye occupied area among the added dyes. Multilayer adsorption: A state in which the amount of dye chromophore adsorbed per unit particle surface area is even larger than the saturated coating amount. Number of adsorbed layers: The amount of dye chromophore adsorbed per unit particle surface area based on the amount of one-layer saturated coating.

The distribution of the light absorption intensity between particles can be expressed as a coefficient of variation of the light absorption intensity of 100 or more particles randomly measured using a microspectroscopy method. Coefficient of variation is 10
It is calculated as 0 × standard deviation / average (%). Since the light absorption intensity is a value proportional to the amount of dye adsorbed, the distribution of light absorption intensity between particles may be rephrased as the distribution of dye adsorption amount between particles. The coefficient of variation of the interparticle distribution of light absorption intensity is preferably at most 60%, more preferably at most 30%, particularly preferably at most 10%. Maximum value of sensitizing dye absorption Am
The variation coefficient of the interparticle distribution at the interval between the shortest wavelength and the longest wavelength indicating 50% of ax is preferably 30% or less,
It is more preferably at most 10%, particularly preferably at most 5%. Further, with respect to the absorption maximum wavelength of the sensitizing dye for each particle, it is preferred that 70% or more, more preferably 90% or more of the particles of the projected area have an absorption maximum in a wavelength range of 10 nm or less. Still more preferably, the absorption maximum wavelength of the sensitizing dye for each grain is preferably 50% or more of the projected area, more preferably 70% or more,
It is particularly preferable that 90% or more of the particles have an absorption maximum in a wavelength range of 5 nm or less.

It is known that the distribution of light absorption intensity (amount of dye adsorbed) between particles becomes uniform with an increase in the amount of dye adsorbed when the adsorption site is fixed on the surface of silver halide grains. In the case of the multi-layer adsorption of the present invention, the adsorption site is not limited as long as it is possible to adsorb several layers as well as two layers. It was found that the distribution was likely to occur. As a result of the analysis, when the ratio of the interaction energy between the second-layer dye and the total adsorption energy of the second-layer dye increases (the ratio of the interaction energy between the first-layer and second-layer dye molecules relatively decreases). It has been found that the dye adsorption amount of the multilayer adsorption system tends to be uneven among particles.
The interaction energy between the first and second layer dye molecules is preferably 20 to the total adsorption energy of the second layer dye.
%, More preferably 40% or more.

In order to enhance the interaction between the first-layer dye and the second-layer dye, electrostatic interaction, van der Waals interaction, hydrogen bond, and coordination bond between the first- and second-layer dye molecules are required. It is preferable to utilize the combined interaction force of these. The main interaction between the dyes in the second layer is preferably van der Waals interaction between the dye chromophores, but as long as the above preferable relationship is satisfied, electrostatic interaction, Van der Waals interaction, hydrogen bonding It is also preferred to utilize coordination bonds and their complex interactions. The ratio of the interaction energy between the first-layer and second-layer dye molecules to the total adsorption energy of the second-layer dye is difficult to determine in practice, but is estimated using computer chemistry techniques such as molecular force field calculations. I can do it. Further, experimentally, the aggregation energies of the second-layer dye molecules and between the first-layer dye molecules and the second-layer dye molecules were measured, and 100
X Aggregation energy of first-layer dye and second-layer dye molecules / (aggregation energy of second-layer dye molecules + aggregation energy of first-layer dye and second-layer dye molecules) can also be estimated. The cohesive energy can be determined, for example, by the method of Matsubara and Tanaka et al. (Journal of the Photographic Society of Japan, 52, 395, 1989).

In the emulsion containing silver halide photographic emulsion grains having a light absorption intensity of 60 or 100 or more, the maximum value Amax of the spectral absorption by the sensitizing dye and the shortest value showing 50% of the maximum value Smax of the spectral sensitivity, respectively. The interval between the wavelength and the longest wavelength is preferably 120 nm or less, more preferably 100 nm or less. 80% of Amax and Smax
The distance between the shortest wavelength and the longest wavelength indicating
It is at least 100 nm, preferably at most 100 nm, more preferably at most 80 nm, particularly preferably at most 50 nm. Further, the interval between the shortest wavelength and the longest wavelength which represent 20% of Amax and Smax is preferably 180 nm or less, more preferably 150 nm or less, and particularly preferably 120 nm.
Or less, most preferably 100 nm or less. The longest wavelength showing a spectral absorption of 50% of Amax or Smax is preferably 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm.

The maximum spectral absorption wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the maximum spectral absorption wavelength is 500 n
A preferred first method for realizing silver halide grains having a light absorption intensity of 100 or more at m or more is a method using the following specific dye.

For example, JP-A-10-239789, JP-A-8
-269,092 and 10-123650, JP-A-8-
Dyes having an aromatic group described in 328189;
A method using a combination of a cationic dye having an aromatic group and an anionic dye; a method using a dye having a multivalent charge described in JP-A-10-171588;
A method using a dye having a pyridinium group described in No. 4774, a method using a dye having a hydrophobic group described in JP-A-10-186559,
197980, a method using a dye having a coordination bonding group, and Japanese Patent Application Nos. 11-63588, 11
-80141, 11-159731, 11-1
No. 59730, No. 11-171324, No. 11-22
No. 1479, No. 11-265768, No. 11-260
No. 643, No. 11-331571, No. 11-3315
No. 70, No. 11-311039, No. 11-33156
7, No. 11-3477781, Japanese Patent Application No. 2000-189.
A method using a specific dye described in No. 66 is preferable.

A particularly preferred method is a method using a dye having at least one aromatic group. Among them, preferably a positively charged dye, a dye whose charge is offset in the molecule, or a method using only a dye having no charge, or a combination of a positively and negatively charged dye, and positive and negative In this method, at least one of the charged dyes uses a dye having at least one aromatic group as a substituent.

The aromatic group will be described in detail. Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are a group having a polycyclic fused ring in which a hydrocarbon aromatic ring and a heteroaromatic ring are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined. And may be substituted with a substituent V described below. As the aromatic ring contained in the aromatic group, preferably, benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine,
Pyrimidine, pyridazine, indolizine, indole,
Benzofuran, benzothiophene, isobenzofuran,
Examples include quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxatiin, phenothiazine, phenazine and the like.

More preferably, they are the above-mentioned hydrocarbon aromatic rings, particularly preferably benzene and naphthalene, and most preferably benzene.

Examples of the dye include those described above as examples of the dye chromophore. Preferably, the dyes mentioned as examples of the polymethine dye chromophore described above are used.

More preferably, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes , Squarium dye, croconium dye, azamethine dye, more preferably cyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye,
Particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

Particularly preferred methods will be described in detail with reference to structural formulas.

That is, the following cases (1) and (2) are preferable. In (1) and (2), (2) is more preferable. (1) A method using at least one of cationic, betaine, and nonionic methine dyes represented by the following general formula (I). (2) A method in which at least one of the cationic methine dyes represented by the following general formula (I) and at least one of the anionic methine dyes represented by the following general formula (II) are simultaneously used. General formula (I)

[0040]

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In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁ is an alkyl group, an aryl group, or a heterocyclic group. Q ₁ represents a group necessary for the compound represented by the general formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Where Z
₁ , R ₁ , Q ₁ , L ₁ , and L ₂ have a substituent in which the methine dye represented by the general formula (I) as a whole becomes a cationic dye, a betaine dye, or a nonionic dye.
However, when the general formula (I) is a cyanine dye or rhodacyanine dye, it preferably has a substituent that becomes a cationic dye. M ₁ represents a counter ion for charge balancing, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. General formula (II)

[0042]

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In the formula, Z ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₂ is an alkyl group, an aryl group, or a heterocyclic group. Q ₂ represents a group necessary for the compound represented by formula (II) to form a methine dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. Where Z
₂ , R ₂ , Q ₂ , L ₃ and L ₄ have a substituent in which the methine dye represented by the general formula (II) as a whole becomes an anion dye. M ₂ represents a counter ion for charge balancing, and m ₂ represents a number of 0 or more necessary to neutralize the charge of the molecule.

However, when the compound of the general formula (I) is used alone, R ₁ is preferably a group having an aromatic ring.

Further, the compound of the general formula (I) and the compound of the general formula (II)
When the compound of the formula ( ₁ ) is used in combination, at least one of R ₁ and R ₂ is preferably a group having an aromatic ring. More preferably, both R ₁ and R ₂ are groups having an aromatic ring.

The cationic dye of the present invention may be any dye in which the charge of the dye excluding the counter ion is cationic, but is preferably a dye having no anionic substituent. The anionic dye of the present invention may be any dye having an anionic charge except for a counter ion, but is preferably a dye having at least one anionic substituent. The betaine dye of the present invention is a dye that has a charge in the molecule but forms an intramolecular salt, and the molecule has no charge as a whole. With the nonionic dye of the present invention,
A dye that has no charge in the molecule.

The term "anionic substituent" as used herein refers to a substituent having a negative charge, for example, a proton-dissociable acidic group dissociated by 90% or more between pH 5 and 8. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group,
And a phosphate group and a borate group. In addition, -CO
NHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a phenolic hydroxyl group, etc., these pka And the surrounding pH, a group from which a proton is dissociated. More preferably a sulfo group, a carboxyl group, -CONHSO ₂ - group, -CON
HCO- group, -SO ₂ NHSO ₂ - a group. Note that-
CONHSO ₂ — group, —CONHCO— group, —SO ₂ N
The HSO ₂ — group, due to its pka and surrounding pH,
In some cases, the proton does not dissociate, and in this case, it is not included in the anionic substituent described herein. That is, when the proton does not dissociate, for example, the general formula (I-1)
Even if two of these groups are substituted for the dye represented by the formula (2), it can be regarded as a cationic dye. Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.

The dye represented by the general formula (I) is more preferably represented by the following general formulas (I-1), (I-2) and (I-3). General formula (I-1)

[0049]

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In the general formula (I-1), L ₅ , L ₆ , L ₇ , L
₈ , L ₉ , L ₁₀ and L ₁₁ represent a methine group. p ₃ and p ₄ represent 0 or 1. n ₁ represents 0, ₁ , 2, 3 or 4. Z ₃ and Z ₄ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₃ and R ₄ are an alkyl group, an aryl group,
Or a heterocyclic group. M ₁ and m ₁ have the same meanings as in formula (I). However, R ₃ , R ₄ , Z ₃ , Z ₄ , L _{5 to} L ₁₁ are
When (I-1) is a cationic dye, it has no anionic substituent, and when (I-1) is a betaine dye, it has one anionic substituent.

Formula (I-2)

[0052]

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In the formula (I-2), L₁₂, L₁₃, L₁₄, And L_Fifteen
Represents a methine group. p_FiveRepresents 0 or 1. q₁ Is 0 or
Represents 1. n_Two Represents 0, 1, 2, 3 or 4. Z_Five
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z₆ And Z₆’Is (N-R₆ ) Q₁ Together with a heterocycle,
Or a group of atoms necessary to form an acyclic acidic end group
Represents Where Z_Five , And Z₆ And Z₆Is fused to the ring
May be. R_Five And R₆ Is an alkyl group, aryl
Represents a group or a heterocyclic group. M₁ , M₁ Is the same as in general formula (I)
Righteous. Where R_Five , R₆ , Z_Five , Z₆ , L₁₂~ L_Fifteen
Is a cationic substituent when (I-2) is a cationic dye
And when (I-2) is a betaine dye, cationic substitution
(I-2) has one group and one anionic substituent.
In the case of on-dye, cationic substituent and anionic substituent
No groups. General formula (I-3)

[0054]

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In the formula (I-3), L₁₆, L₁₇, L₁₈, L₁₉, L
₂₀, L_{twenty one}, L_{twenty two}, L_{twenty three}, And L_{twenty four}Represents a methine group. p
₆ And p₇ Represents 0 or 1. q_TwoRepresents 0 or 1.
n_Three And n_Four Represents 0, 1, 2, 3 or 4. Z₇ ,
And Z₉ Is a group of atoms necessary to form a nitrogen-containing heterocycle.
Represent. Z₈ And Z₈’Is (N-R₈ ) Q_Two Together with
Represents an atom group necessary for forming a heterocyclic ring. However,
Z₇ , Z₈ And Z₈’, And Z₉ Has a ring fused
Is also good. R₇ , R₈ And R₉ Is an alkyl group, aryl
Represents a group or a heterocyclic group. M₁ , M₁ Is the same as in general formula (I)
Righteous. Where R ₇ , R₈ , R₉ , Z₇ , Z₈ , Z
₉ , L₁₆~ L_{twenty four}Is an anion when (I-3) is a cationic dye
When (I-3) is a betaine dye without a functional substituent,
It has one nonionic substituent.

Further, as the anionic dye represented by the general formula (II), more preferably, the following general formula (II-1):
This is the time represented by (II-2) and (II-3). General formula (II-1)

[0057]

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In the general formula (II-1), L ₂₅ , L ₂₆ , L ₂₇ , L
₂₈ , L ₂₉ , L ₃₀ and L ₃₁ represent a methine group. p ₈ and p ₉ represent 0 or 1. n ₅ represents 0, 1, 2, 3 or 4. Z ₁₀ and Z ₁₁ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁₀ and R ₁₁ are an alkyl group, an aryl group,
Or a heterocyclic group. M ₂ and m ₂ have the same meanings as in formula (II). However, R ₁₀ and R ₁₁ have an anionic substituent.

Formula (II-2)

[0060]

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In the formula (II-2), L ₃₂ , L ₃₃ , L ₃₄ and L
₃₅ represents a methine group. p ₉ represents 0 or 1. q ₃ 0
Or represents 1. n ₆ represents 0, 1, 2, 3, or 4. Z
₁₂ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁₃ and Z ₁₃ ′ represent an atomic group necessary for forming a heterocyclic or acyclic acidic terminal group together with (NR ₁₃ ) q ₃ . However, a ring may be condensed to Z ₁₂ and Z ₁₃ and Z ₁₃ ′. R ₁₂ and R ₁₃ represent an alkyl group, an aryl group, or a heterocyclic group. M ₂ and m ₂ are represented by the general formula (I
Synonymous with I). However, at least one of R ₁₂ and R ₁₃ has an anionic substituent. General formula (II-3)

[0062]

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In the formula (II-3), L ₃₆ , L ₃₇ , L ₃₈ , L ₃₉ ,
_{L 40, L 41, L 42} , L 43, and L ₄₄ each represents a methine group.
p ₁₀ and p ₁₁ each represents 0 or 1. q ₄ is 0 or 1. n ₇ and n ₈ represent 0, 1, 2, 3 or 4.
Z ₁₄ and Z ₁₆ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₁₅ and Z ₁₅ ′ represent an atom group necessary for forming a heterocyclic ring together with (N—R ₁₅ ) q ₄ .
However, a ring may be condensed in Z ₁₄ , Z ₁₅ and Z ₁₅ ′, and Z ₁₆ . R ₁₄ , R ₁₅ and R ₁₆ represent an alkyl group, an aryl group, or a heterocyclic group. M ₂ and m ₂ have the same meanings as in formula (II). However, at least two of R ₁₄ , R ₁₅ , and R ₁₆ have an anionic substituent.

However, when the compounds of the general formulas (I-1), (I-2) and (I-3) are used alone, at least one, preferably both of R ₃ and R ₄ are aromatic rings. group having, R ₅
And at least one of R ₆ , preferably a group having an aromatic ring, and at least one, preferably two, and more preferably at least three of R ₇ , R ₈ , and R _9. Is a group having

When the compounds of the general formulas (I-1), (I-2) and (I-3) are used in combination with the compounds of the general formulas (II-1), (II-2) and (II-3) Represents R _{3 to} R ₉ , and R ₁₀ to
At least one of R ₁₆ is a group having an aromatic ring, preferably two are groups having an aromatic ring, more preferably three are groups having an aromatic ring, and particularly preferably four The above is the group having an aromatic ring.

According to the above preferred method, the light absorption intensity is 60 or more when the maximum wavelength of spectral absorption is less than 500 nm, or the light absorption intensity is 1 or more when the maximum wavelength of spectral absorption is 500 nm or more.
Although silver halide grains of 00 or more can be realized, the dye in the second layer is usually adsorbed in a monomer state,
In most cases, the width will be wider than the desired absorption width and spectral sensitivity width. Therefore, in order to realize high sensitivity in a desired wavelength range, it is necessary to form a J-aggregate in the dye adsorbed in the second layer. Furthermore, since the J-aggregate has a high fluorescence yield and a small Stokes shift, it is also preferable for transmitting the light energy absorbed by the second-layer dye to the first-layer dye having a close light absorption wavelength by Forster type energy transfer. .

In the present invention, the dye of the second layer or more is
A dye adsorbed on silver halide grains but not directly adsorbed on silver halide. In the present invention, the J-aggregate of the dye of the second layer or more, the absorption width on the long wavelength side of the absorption indicated by the dye adsorbed in the second or more layers, the monomer state of no interaction between the dye chromophore It is defined as not more than twice the absorption width of the long wavelength side of the absorption exhibited by the dye solution. Here, the absorption width on the long wavelength side indicates an energy width between an absorption maximum wavelength and a wavelength that is longer than the absorption maximum wavelength and exhibits an absorption of 1/2 of the absorption maximum. It is generally known that when a J-aggregate is formed, the absorption width on the longer wavelength side becomes smaller than that in the monomer state. When adsorbed to the second layer in the monomer state,
Due to the non-uniformity of the adsorption position and the state, the absorption width becomes twice or more the absorption width on the long wavelength side in the monomer state of the dye solution.
Therefore, a J-aggregate of the dye of the second layer or more can be defined by the above definition.

The spectral absorption of the dye adsorbed on the second and higher layers is
It can be determined by subtracting the spectral absorption of the first-order dye from the total spectral absorption of the emulsion. Spectral absorption by the first-layer dye can be determined by measuring the absorption spectrum when only the first-layer dye is added. In addition, by adding a dye desorbing agent to the emulsion in which the sensitizing dye is adsorbed in multiple layers to desorb the dyes in the second or more layers, the spectral absorption spectrum of the first-layer dye can be measured. In experiments in which a dye is desorbed from the particle surface using a dye desorbing agent, the first-layer dye is usually desorbed after the second or more layers of dye are desorbed. Can be requested. This makes it possible to determine the spectral absorption of the dyes in the second and higher layers. The method using a pigment desorbent is
Report by Asanuma et al. (Journal of Physical Chemistry B)
Chemistry B), Vol. 101, pp. 2149 to 2153 (1997)).

To form a J-aggregate of a second-layer dye using a cationic dye, a betaine dye, or a nonionic dye represented by the general formula (I) and an anionic dye represented by the general formula (II) Preferably, the dye to be adsorbed as the first layer and the dye to be adsorbed to the second and subsequent layers are separately added, and it is more preferable to use dyes having different structures for the first-layer dye and the second-layer and higher dyes. It is preferable to add a cationic dye, a betaine dye, or a nonionic dye alone or a combination of a cationic dye and an anionic dye to the second and subsequent dyes.

As the first-layer dye, any dye can be used. Preferably, the compound represented by the general formula (I) or (I)
It is a dye represented by I), and more preferably a dye represented by the general formula (I). As the second layer dye, it is preferable to use the cationic dye, the betaine dye or the nonionic dye of the general formula (I) alone. Further, when a cationic dye and an anionic dye are used in combination as a preferred second layer dye in the same row, it is preferable that one of the two is a cationic dye of the general formula (I) or an anionic dye of the general formula (II), Further, it is preferable to include both the cationic dye of the general formula (I) and the anionic dye of the general formula (II). The ratio of the cationic dye / anionic dye as the second layer dye is preferably 0.5 to 2, more preferably 0.75 to 1.33, and most preferably 0.9 to 1.
11 range.

In the present invention, a dye other than the dye represented by the general formula (I) or (II) may be added.
The dye represented by the general formula (I) or (II) is preferably at least 50%, more preferably at least 70%, most preferably at least 90% of the total amount of the dye added.
By adding the second-layer dye in this way, the interaction between the second-layer dyes can be enhanced while promoting rearrangement of the second-layer dyes, so that a J-aggregate can be formed.

In the dye of the general formula (I) or the general formula (II), when used as the first layer dye,
Z ₁ and Z ₂ are preferably a basic nucleus substituted with an aromatic group or a basic nucleus condensed with three or more rings. When used as a dye for the second or higher layer, Z ₁ and Z ₂ are preferably basic nuclei condensed with three or more rings.

The number of condensed rings of the basic nucleus is, for example, 2 for the benzoxazole nucleus and 3 for the naphthoxazole nucleus. Even when the benzoxazole nucleus is substituted with a phenyl group, the number of condensed rings is 2. The basic nucleus condensed with three or more rings is not particularly limited as long as it is a polycyclic condensed heterocyclic basic nucleus condensed with three or more rings.
Cyclic condensed heterocyclic rings and tetracyclic condensed heterocyclic rings are included. As the tricyclic condensed heterocyclic ring, naphtho [2,3-
d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole,
Naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-d] imidazole, Naft [2,3-
d] selenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3- d]
Oxazole, indolo [5,6-d] thiazole, indolo
[6,5-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6
-d] oxazole, benzothieno [6,5-d] oxazole, benzothieno [2,3-d] oxazole and the like. Further, as the tetracyclic fused ring heterocycle, preferably anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,1-d] oxazole, anthra [2,3-
d] Thiazole, anthra [1,2-d] thiazole, phenanthro [2,1-d] thiazole, phenanthro [2,3-d] imidazole, anthra [1,2-d] imidazole, anthra
[2,1-d] imidazole, anthra [2,3-d] selenazole, phenanthro [1,2-d] selenazole, phenanthro
[2,1-d] selenazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro
[2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2
-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, benzofuro [5,6-d] oxazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2] -d] oxazole, tetrahydrocarbazolo [6,7-d] oxazole, tetrahydrocarbazolo
[7,6-d] oxazole, dibenzothieno [2,3-d] thiazole, dibenzothieno [3,2-d] thiazole, tetrahydrocarbazolo [6,7-d] thiazole and the like. More preferably, the basic nucleus fused with three or more rings is naphtho.
[2,3-d] oxazole, naphtho [1,2-d] oxazole,
Naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, indolo [5,6-d] oxazole, Indoro [6,5-
d] oxazole, indolo [2,3-d] oxazole, indolo [5,6-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5
-d] oxazole, benzofuro [2,3-d] oxazole,
Benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, Anthra [2,3-d] thiazole, anthra [1,2-d] thiazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, Dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro
[3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2-d] oxazole, and particularly preferably naphtho [2,3-d] oxazole and naphtho [1 , 2-d] oxazole, naphtho [2,3-d] thiazole, indolo [5,6-d] oxazole, indolo [6,5-d]
Oxazole, indolo [5,6-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6]
-d] oxazole, carbazolo [2,3-d] oxazole,
Carbazolo [3,2-d] oxazole, dibenzofuro [2,3-
d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-
d] Thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-
d] oxazole and dibenzothieno [3,2-d] oxazole.

Another preferable method for realizing an adsorption state in which a dye chromophore is coated in multiple layers on the surface of a silver halide grain is to form two or more dye chromophores linked by a covalent bond by a linking group. This is a method using a dye compound having a group moiety. The dye chromophore that can be used is not particularly limited, and examples thereof include those described above for the dye chromophore. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. More preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, particularly preferably cyanine dyes,
Rhodocyanine dyes and merocyanine dyes, most preferably cyanine dyes.

As a preferable example, see, for example,
No. 265144, a method using a dye linked by a methine chain, a method described in JP-A-10-226758, a method using a dye linked to an oxonol dye, JP-A-10-110107, and JP-A-10-30735.
8, Nos. 10-307359 and 10-310715, the method using a linking dye having a specific structure, and the specific linking groups described in Japanese Patent Application Nos. 8-31212 and 10-204306. Using linked dyes, Japanese Patent Application Nos. 11-34444 and 11-34463.
And a method using a linked dye having a specific structure described in JP-A-11-34462, and a linked dye is formed in an emulsion using a dye having a reactive group described in Japanese Patent Application No. 10-249971. And the like.

A preferable linking dye is a dye represented by the following formula (III). General formula (III)

[0077]

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In the formula, D ₁ and D ₂ represent a dye chromophore. La represents a linking group or a single bond. q and r each represent an integer from 1 to 100. M ₃ represents a charge balancing counter ion, and m ₃ represents a number required to neutralize the charge of the molecule.

Next, D ₁ , D ₂ and La will be described.

The dye chromophore represented by D ₁ and D ₂ may be any. Specifically, those described above for the dye chromophore can be used. Preferably, it is the polymethine dye chromophore represented by the aforementioned dye chromophore. More preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, most preferred are cyanine dyes. The general formula of a preferred dye is described in US Pat. No. 5,994,051.
Nos. 32 to 36, and U.S. Pat.
47, 236, pp. 30-34. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21 to 22, (XI), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or more). Below)).

In the present invention, when the linking dye represented by the general formula (III) is adsorbed on silver halide grains,
₂ is preferably a chromophore not directly adsorbed on silver halide. That is, the suction force of the silver halide grains of D ₂ is preferably those with sensitive than D _1. Further, order of adsorption strength to a silver halide grain is, if a D _1> La> D ₂ being most preferred.

As described above, D ₁ is preferably a sensitizing dye moiety having adsorptivity to silver halide grains.
It may be adsorbed by either physical adsorption or chemical adsorption.

D ₂ has a low adsorptivity to silver halide grains and is preferably a luminescent dye. As the kind of the luminescent dye, those having a skeleton structure of a dye used for a dye laser are preferable. These are, for example, Maeda Mitsuo,
Laser Studies, 8, 694, 803, 958 (1980) and 9, 85 (1981), and by F. Sehaefer, "Dye Lasers", Springer (197).
3 years).

Further, it is preferable that the maximum absorption wavelength of D _{1 in} the silver halide photographic material is longer than the maximum absorption wavelength of D ₂ . Further, the emission of D ₂ is D ₁
Preferably overlap with the absorption of. Further, D ₁ preferably forms a J-aggregate. Further, in order for the linked dye represented by the general formula (I) to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that D ₂ also forms a J-aggregate.

The reduction potential and oxidation potential of D ₁ and D ₂ may be any values, but the reduction potential of D ₁ is more noble than the value obtained by subtracting 0.2 v from the reduction potential of D _2. Is preferred.

La is a linking group (preferably a divalent linking group)
Or, represents a single bond. The linking group preferably comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably, an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an arylene group (eg, phenylene, naphthylene), an alkenylene group (eg, ethenylene, propenylene), an alkynylene group (eg, ethinylene, propynylene), an amide group, an ester Group, sulfoamide group, sulfonic ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (Va)-(Va is a hydrogen atom,
Or a monovalent substituent. Examples of the monovalent substituent include V described below. ), A heterocyclic divalent group (for example, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-
A diyl group) in combination with one or more carbon atoms.
Represents a linking group of 0 or less.

The above linking group may further have a substituent represented by V described below. In addition, these linking groups may contain a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle).

More preferably, the alkylene group has 1 to 10 carbon atoms (eg, methylene, ethylene, propylene,
Butylene), an arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), an alkenylene group having 2 to 10 carbon atoms (eg, for example, ethenylene, propenylene), an alkynylene group having 2 to 10 carbon atoms (eg, Ethynylene, propynylene), ether group,
It is a divalent linking group having 1 to 10 carbon atoms formed by combining one or more of an amide group, an ester group, a sulfoamide group, and a sulfonic ester group. They are,
It may be replaced by V described later.

La is a linking group which may perform energy transfer or electron transfer by through-bond interaction. The through-bond interaction includes a tunnel interaction and a super-exchange interaction. Among them, a through-bond interaction based on a super-exchange interaction is preferable. Through-bond and super-exchange interactions are described by Shammai Speiser.
Author, Chemical Review (Chem. Rev.) Vol. 96, No. 1960
-Interaction as defined on page 1963, 1996. Linking groups that transfer energy or electrons by such interaction include Shammai Spacer (Shammai Spacer).
Speiser), Chemical Review (Chem. Rev.) No. 96
Vol., Pp. 1967-1969, 1996.

Q and r represent an integer from 1 to 100. It is preferably an integer of 1 to 5, more preferably an integer of 1 to 2, and particularly preferably 1. q
And when r is 2 or more, a plurality of La and D ₂ contained therein may be respectively different linking groups and dye chromophores.

The dye of the general formula (III) preferably has a charge of -1 as a whole.

More preferably, in the general formula (III), D ₁ and D ₂ are each independently the following general formula (IV):
This is the time when the methine dye is represented by (V), (VI) or (VII). General formula (IV)

[0093]

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In the formula (IV), L ₄₅ , L ₄₆ , L ₄₇ , L ₄₈ , L
₄₉ , L ₅₀ and L ₅₁ represent a methine group. p ₁₂ and p ₁₃
Represents 0 or 1. n ₉ represents 0, 1, 2, 3, or 4. Z ₁₇ and Z ₁₈ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. M ₄ represents a charge balancing counter ion, and m ₄ represents a number of 0 or more necessary to neutralize the charge of the molecule. R ₁₇ and R ₁₈ represent an alkyl group, an aryl group, or a heterocyclic group. General formula (V)

[0095]

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In the formula (V), L ₅₂ , L ₅₃ , L ₅₄ and L ₅₅ represent a methine group. p ₁₄ represents 0 or 1. q ₅ represents 0 or 1. n ₁₀ represents 0, 1, 2, 3 or 4. Z ₁₉
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z ₂₀ and Z ₂₀ 'represents an atomic group necessary to form a (N-R ₂₀₎ q ₅ and together heterocyclic ring or an acyclic acidic terminal groups. However, a ring may be condensed to Z ₁₉ , and Z ₂₀ and Z ₂₀ ′. M ₅ represents a charge balancing counter ion, m ₅
Represents a number of 0 or more necessary to neutralize the electric charge of the molecule.
R ₁₉ and R ₂₀ represent an alkyl group, an aryl group, or a heterocyclic group. General formula (VI)

[0097]

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In the formula (VI), L ₅₆ , L ₅₇ , L ₅₈ , L ₅₉ , L
₆₀ , L ₆₁ , L ₆₂ , L ₆₃ and L ₆₄ represent a methine group. p ₁₅
And p ₁₆ represents 0 or 1. q ₆ represents 0 or 1.
n ₁₁ and n ₁₂ represent 0, 1, 2, 3 or 4. Z ₂₁ and Z ₂₃ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. Z ₂₂ and Z ₂₂ ′ represent an atomic group necessary for forming a heterocyclic ring together with (N—R ₂₂ ) q ₆ . However,
Rings may be fused to Z ₂₁ , Z ₂₂ and Z ₂₂ ′, and Z ₂₃ . M ₆ represents a charge-balancing counter ion, and m ₆ represents a number of 0 or more required to neutralize the charge of the molecule. R ₂₁ , R ₂₂ and R ₂₃ represent an alkyl group, an aryl group, or a heterocyclic group.

Formula (VII)

[0100]

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In the formula (VII), L₆₅, L₆₆, And L₆₇Is meth
Represents a group. q₇ And q₈ Represents 0 or 1. n₁₃Is
Represents 0, 1, 2, 3 or 4. Z_{twenty four}And Z_{twenty four}’Is (N-R
_{twenty four}) Q ₇Together with and Z_{twenty five}And Z_{twenty five}’Is (N−
R_{twenty five}) Q₈ Together with a heterocyclic or acyclic acid
Represents the group of atoms necessary to form a terminal group. However,
Z_{twenty four}And Z_{twenty four}’And Z_{twenty five}And Z_{twenty five}’Even if the ring is fused
good. M₇ Represents a charge-balancing counter ion, m₇ Is the molecular charge
Represents the number of zero or more necessary to neutralize the load. R_{twenty four},as well as
R_{twenty five}Represents an alkyl group, an aryl group, or a heterocyclic group.

D _{1 in the} general formula (III) is preferably a methine dye represented by the above-mentioned general formulas (IV), (V) and (VI), and more preferably D _{1 in} the general formula (IV) This is the case for methine dyes. D _{2 in the} general formula (III) is preferably a methine dye represented by the above general formulas (IV), (V), and (VII), and more preferably D ₂ in the general formula (I)
V) and methine dyes represented by (V), particularly preferably methine dyes represented by the general formula (IV).

A method using the above general formulas (I) and (II),
Among the methods using the general formula (III), the methods using the general formulas (I) and (II) are more preferable.

Hereinafter, the general formula (I) (including (I-1,2,3)),
The methine compounds represented by (II) (including (II-1,2,3)), (IV), (V), (VI) and (VII) will be described in detail.

In the general formulas (I) and (II), Q ₁ and Q ₂
Represents a group necessary for forming a methine dye. Although any methine dye can be formed by Q ₁ and Q ₂ , the methine dye shown as an example of the dye chromophore described above can be used.

Preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FM Harme
r) `` Heterocyclic Compounds-Cyanine Soybeans and Related Compounds (Heterocyc
lic Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
&amp; Sons), New York, London, 1964, DMSturmer, Heterocyclic Compound Special Topics in Heterocyclic Chemistry
lic Compounds-Special topics in heterocyclic chemi
stry) ", Chapter 18, Section 14, 482-515. Preferred general formulas of the dyes include the general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
General formulas described on pages 0 to 34 are exemplified. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694, Nos. 21 and 2.
(XI), (XII), and (XIII) in column 2 (however, the number of n12, n15, n17, and n18 is not limited;
Or more integers (preferably 4 or less). In the general formulas (I) and (II), when a cyanine dye or rhodacyanine dye is formed by Q ₁ and Q _2, it can be represented by the following resonance formula. General formula (I)

[0107]

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General formula (II)

[0109]

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The general formulas (I), (II), (IV), (V) and
And (VI), Z₁ , Z_Two , Z_Three , Z _Four , Z_Five , Z₇ , Z
₉ , Z_Ten, Z₁₁, Z₁₂, Z₁₄, Z₁₆, Z₁₇, Z₁₈,
Z₁₉, Z _{twenty one}, And Z_{twenty three}Is a nitrogen-containing heterocyclic ring, preferably 5 or
Represents the atoms required to form a 6-membered nitrogen-containing heterocyclic ring.
You. However, the rings may be condensed with these. As a ring
May be an aromatic ring or a non-aromatic ring. Like
Or an aromatic ring such as a benzene ring or naphthalene
Aromatic ring such as ring, pyrazine ring, thiophene
And a heteroaromatic ring such as a ring.

Examples of the nitrogen-containing heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus,
Selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-
Quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3
-Isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like,
Preferably, a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3
-Dimethylindolenine), benzimidazole nucleus, 2
-Pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-
A quinoline nucleus, a 1-isoquinoline nucleus and a 3-isoquinoline nucleus, more preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), and a benzimidazole nucleus. Particularly preferred are a benzoxazole nucleus, a benzothiazole nucleus and a benzimidazole nucleus, and most preferred are a benzoxazole nucleus and a benzothiazole nucleus.

Assuming that the substituent on these nitrogen-containing heterocycles is V, the substituent represented by V is not particularly limited.
For example, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (also referred to as a heterocyclic group) Good), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group ( Anilino group), an acylamino group, an aminocarbonylamino group,
An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, Alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups. More specifically, V is a halogen atom (eg,
A chlorine atom, a bromine atom, an iodine atom) and an alkyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkyl group; They include an alkyl group (preferably having 1 to 3 carbon atoms).
An alkyl group of 0, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 carbon atoms) 30 substituted or unsubstituted cycloalkyl groups such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, It is a monovalent group obtained by removing one hydrogen atom from bicycloalkane of formulas 5 to 30. For example, bicyclo [1,2,2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl ) And a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl,
Geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms) For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 carbon atoms)
To 30 substituted or unsubstituted bicycloalkenyl groups, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, it includes bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) Is a monovalent group obtained by removing one hydrogen atom from, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, -Pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl, alkoxy (preferably Ku is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, t-butoxy,
n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably carbon A substituted or unsubstituted heterocyclic oxy group of the number 2 to 30, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted group of 2 to 30 carbon atoms) A substituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy,
Benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom)
To 30 substituted or unsubstituted carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyl Oxyphenoxycarbonyloxy), an amino group (preferably,
An amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, Diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino Acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably having 1 to 3 carbon atoms)
0-substituted or unsubstituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted alkoxycarbonylamino group, for example,
Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having no carbon atoms)
To 30 substituted or unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably carbon Substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-tri Chlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), Ali Lucio group (preferably having a carbon number of 6
To 30 substituted or unsubstituted arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, , 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3
-Dodecyloxypropyl) sulfamoyl, N, N-
Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms) Or an unsubstituted alkylsulfinyl group, 6 to 30 substituted or unsubstituted arylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to 30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl Groups (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-
Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyl) Oxycarbonyl), carbamoyl group (preferably,
A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl,
N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms;
A substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably
A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms; For example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyl Oxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino ), A silyl group (preferably having 3 carbon atoms) 0 substituted or unsubstituted silyl group, for example, represents trimethylsilyl, t- butyl dimethylsilyl, phenyldimethylsilyl), a.
Also, a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a quinoline ring , A phenanthrene ring,
Fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring,
Phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring. ) May be condensed.

Among the above functional groups, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such functional groups include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl,
An arylsulfonylaminocarbonyl group is exemplified.
Examples include methylsulfonylaminocarbonyl,
p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

Preferred examples of the substituent are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, aromatic ring condensation, sulfo group, carboxy group and hydroxy group.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z
_{9, Z 10, Z 11,} Z 12, Z 14, and more preferably an aromatic group as a substituent V on Z _16, an aromatic ring condensed.

When the methine dye represented by formula (IV), (V) or (VI) represents the chromophore represented by D ₁ in formula (III), Z ₁₇ , Z ₁₈ , The substituent V on Z ₁₉ , Z ₂₁ , and Z ₂₃ is more preferably an aromatic group or an aromatic ring condensed.

When the methine dye represented by formula (IV), (V) or (VI) represents the chromophore represented by D ₂ in formula (III), Z ₁₇ , Z ₁₈ , The substituent V on Z ₁₉ , Z ₂₁ , and Z ₂₃ is more preferably a carboxy group, a sulfo group, or a hydroxy group, and particularly preferably a sulfo group.

[0118] Z ₆ and Z ₆ 'and _{(N-R 6) q 1} , Z 13 and Z _13' and _{(N-R 13) q 3} , Z 20 and Z _{2 0} 'and (N-
R ₂₀ ) q ₅ , Z ₂₄ and Z ₂₄ ′, (N—R ₂₄ ) q ₇ , and Z
₂₅ , Z ₂₅ ′, and (N—R ₂₅ ) q ₈ together represent an atom group necessary to form a heterocyclic or acyclic acidic terminal group. The heterocyclic ring (preferably a 5- or 6-membered heterocyclic ring) may be any, but an acidic nucleus is preferred. Next, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nucleus and acyclic acid end groups can take the form of the acidic nucleus and acyclic acid end groups of any common merocyanine dye. Z in the preferred form
₆ , Z ₁₃ , Z ₂₀ , Z ₂₄ and Z ₂₅ are thiocarbonyl, carbonyl, ester, acyl, carbamoyl, cyano and sulfonyl, more preferably thiocarbonyl and carbonyl. Z ₆ ', Z ₁₃ ', Z
₂₀ ′ and Z ₂₄ ′ represent the remaining atomic group necessary to form an acidic nucleus and an acyclic acidic terminal group. When forming an acyclic acidic terminal group, preferably a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group,
And a cyano group and a sulfonyl group.

Q ₁ , q ₃ , q ₅ , q ₇ and q ₈ are 0 or 1, but preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to herein are described, for example, in "Theory of the Photographic Process", edited by James.
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, 198-200. Here, the acyclic acidic terminal group means an acidic, that is, electron-accepting terminal group that does not form a ring. The acidic nucleus and the acyclic acidic end group are, specifically,
U.S. Pat. Nos. 3,567,719, 3,575,86
No. 9, No. 3, 804, 634, No. 3, 837, 862
No. 4,002,480,4,925,777
No. 3,167,546, U.S. Pat.
No. 4,051, and U.S. Pat. No. 5,747,236.

The acidic nucleus forms a heterocycle (preferably a 5- or 6-membered nitrogen-containing heterocycle) consisting of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. And more preferably a 5- or 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Specifically, for example, the following nuclei can be mentioned.

2-pyrazolin-5-one, pyrazolidin-3,5-dione, imidazoline-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one,
2-thiooxazolidin-2,5-dione, 2-thiooxazoline-2,4 dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4 dithione, Isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1dioxide, indoline-2
-On, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo6,7 dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4 Dihydroisoquinolin-4-one, 1,3-dioxane-4,6 dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4 dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3 dione , Pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a]
Benzimidazole, pyrazolopyridone, 1, 2, 3,
4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1
Dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus.

Further, the nucleus having an exomethylene structure in which the carbonyl group or thiocarbonyl group forming the nucleus is substituted at the active methylene position of the acidic nucleus, and a raw material for an acyclic acidic terminal group. A nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene.

The acidic nucleus and the acyclic acidic terminal group may be substituted or condensed with the substituent or ring represented by the substituent V described above.

Z₆ And Z₆ ’And (N-R₆ ) Q₁ , Z₁₃When
Z₁₃’And (N-R₁₃) Q_Three , Z₂₀And Z ₂₀’And (N-
R₂₀) Q_Five , Z_{twenty four}And Z_{twenty four}’And (N-R_{twenty four}) Q₇ , And Z
_{twenty five}And Z_{twenty five}’And (N-R_{twenty five}) Q₈ Preferably as folds
, 2, or 4-thiohydantoin, 2-oxa
Zolin-5-one, 2-thiooxazoline-2,4 di
On, thiazolidine-2,4 dione, rhodanine, thi
Azolidine-2,4-dithione, barbituric acid, 2-
Thiobarbituric acid, more preferably hydan.
Toin, 2 or 4-thiohydantoin, 2-oxazo
Lin-5-one, rhodanine, barbituric acid, 2-chi
Obarbituric acid. Particularly preferably, 2 or 4-
Thiohydantoin, 2-oxazoline-5-one, raw
Danin and barbituric acid.

Z₈ And Z₈ ’And (N-R₈ ) Q_Two , Z_FifteenWhen
Z_Fifteen’And (N-R_Fifteen) Q_Four , And Z_{twenty two}And Z_{twenty two}’And (N-
R_{twenty two}) Q₆ As the heterocyclic ring formed by
Z₆And Z₆ ’And (N-R₆ ) Q₁ , Z₁₃And Z₁₃’And (N
-R₁₃) Q_Three , Z₂₀And Z₂₀’And (N-R₂₀) Q_Five , Z_{twenty four}
And Z_{twenty four}’And (N-R_{twenty four}) Q₇ , And Z_{twenty five}And Z_{twenty five}’And (N
-R_{twenty five}) Q₈ Is the same as described in the description of the heterocyclic ring
No. Preferably, the aforementioned Z₆ And Z₆ ’And (N-R
₆) Q₁ , Z₁₃And Z₁₃’And (N-R₁₃) Q_Three , Z_{Two 0}And Z
₂₀’And (N-R₂₀) Q_Five, Z_{twenty four}And Z_{twenty four}’And (N-R_{twenty four})
q₇ , And Z_{twenty five}And Z _{twenty five}’And (N-R_{twenty five}) Q₈ Of the heterocycle
Removal of oxo or thioxo groups from acidic nuclei described in the description
It was what was.

More preferably, Z ₆ and Z ₆ ′ and (N—R ₆ ) q ₁ , Z ₁₃ and Z ₁₃ ′ and (N—R ₁₃ ) q ₃ ,
Z ₂₀ and Z ₂₀ 'and _{(N-R 20) q 5} , Z 24 and Z _24' and (N
—R ₂₄ ) q ₇ , or an acidic nucleus of Z ₂₅ , Z ₂₅ ′, and (N—R ₂₅ ) q ₈ , which is obtained by removing an oxo group or a thioxo group,

More preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one,
2-thiooxazoline-2,4 dione, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4
Dithione, barbituric acid, 2-thiobarbituric acid is obtained by removing an oxo group or a thioxo group, particularly preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, Oxo group from 2-thiobarbituric acid,
Or those excluding a thioxo group, most preferably 2
Or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine from which an oxo group or a thioxo group is removed.

Each of q ₂ , q ₄ and q ₆ is 0 or 1, but preferably 1.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
_{7, R 8, R 9,} R 10, R 11, R 12, R 13, R 14,
R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ and R ₂₅ are an alkyl group, an aryl group and a heterocyclic group, specifically, for example, a carbon atom having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms. Substituted alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 1
8, preferably 1 to 7, particularly preferably 1 to 4, substituted alkyl groups, for example, the above-mentioned V-substituted alkyl groups as substituents. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-hydroxyethyl, 3-hydroxypropyl), a carboxyalkyl group (eg, 2- Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), an alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl),
Aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoyl Alkyl group (for example, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3 -Sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl groups (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl groups (eg, methanesulfonylcarbamoylmethyl) Group), an acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group), an alkylsulfonylsulfamoylalkyl group (eg, methanesulfonylsulfamoylmethyl) Group)}, 6 to 20 carbon atoms,
It is preferably an unsubstituted aryl group having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms (for example, phenyl group or naphthyl group), 6 to 20 carbon atoms, preferably 6 carbon atoms.
To 10, more preferably a substituted aryl group having 6 to 8 carbon atoms (for example, an aryl group substituted by V described above as an example of the substituent. Specific examples include a p-methoxyphenyl group and a p-methylphenyl An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group). 2,2-pyridyl group, 3-pyrazolyl, 3-isoxazolyl, 3-isothiazolyl, 2-imidazolyl,
-Oxazolyl, 2-thiazolyl, 2-pyridazyl, 2
-Pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl), having 1 to 20 carbon atoms, preferably 3 to 1 carbon atoms
0, and more preferably a substituted heterocyclic group having 4 to 8 carbon atoms (for example, a heterocyclic group substituted by V described above as an example of a substituent. Specifically, a 5-methyl-2-thienyl group, 4-methoxy-2 -Pyridyl group etc.).

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
Preferred as ₈ and R ₉ are groups having an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, and these further include a hydrocarbon aromatic ring,
And a polycyclic fused ring in which heteroaromatic rings are fused together, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined, and may be substituted with the aforementioned substituent V or the like. Is also good. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferred.

Further, the group having an aromatic ring is represented by -Lb-A
It can be represented by ₁ . Here, Lb represents a single bond or a linking group. A ₁ represents an aromatic group. As the linking group for Lb, preferably, the linking group described for La or the like is mentioned. As the aromatic group for A ₁ , those described as examples of the aforementioned aromatic group are preferred.

Preferably, as the alkyl group having a hydrocarbon aromatic ring, an aralkyl group (for example, benzyl,
-Phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), aryloxyalkyl group (for example, 2
-Phenoxyethyl, 2- (1-naphthoxy) ethyl,
2- (4-biphenyloxy) ethyl, 2- (o, m or p-halophenoxy) ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl) and the like. Examples of the alkyl group having a heteroaromatic ring include 2- (2-pyridyl) ethyl and 2- (4-
Pyridyl) ethyl, 2- (2-furyl) ethyl, 2-
(2-thienyl) ethyl and 2- (2-pyridylmethoxy) ethyl are exemplified. 4 as a hydrocarbon aromatic group
-Methoxyphenyl, phenyl, naphthyl, biphenyl and the like. Examples of the heteroaromatic group include a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, and 3-pyrazolyl.

More preferably, the above-mentioned alkyl group having a substituted or unsubstituted hydrocarbon aromatic ring or heteroaromatic ring is used. Particularly preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring.

R ₂ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
Preferred as ₁₅ and R ₁₆ are groups having an aromatic ring. Both R ₁₀ and R ₁₁ and at least one of R ₁₂ and R ₁₃ and at least one of R ₁₄ , R ₁₅ and R ₁₆ have an anionic substituent. R ₂ preferably has an anionic substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring.
Further, it may be a hydrocarbon aromatic ring, a polycyclic fused ring in which heteroaromatic rings are fused together, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined, It may be replaced by V or the like. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferred.

The group having an aromatic ring is represented by -Lc-A
_TwoCan be represented by Here, Lc represents a single bond.
Or a linking group. A_TwoRepresents an aromatic group
You. As the linking group for Lc, preferably, for example, the aforementioned La or the like.
Examples include the linking groups described above. A _TwoGood as an aromatic group for
More preferably, those described as examples of the aromatic group described above are used.
You. Lc or A_TwoHas at least one anionic
It is preferable that the substituent is substituted.

Preferably, the alkyl group having a hydrocarbon aromatic ring is an aralkyl group substituted by a sulfo group, a phosphate group, or a carboxyl group (eg, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl) , 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4'-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), sulfo Aryloxycarbonylalkyl group (3-sulfophenoxycarbonylpropyl) substituted with a group, a phosphate group or a carboxyl group, an aryloxyalkyl group substituted with a sulfo group, a phosphate group or a carboxyl group (for example, 2- (4-
Sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl, 4,4-diphenoxy-3-sulfobutyl), and the like. Examples of the alkyl group having a heteroaromatic ring include 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, and 2- (2-thienyl) -2-sulfopropyl. Propyl and the like. Examples of the hydrocarbon aromatic group include a sulfo group, a phosphoric acid group, and an aryl group substituted with a carboxyl group (eg, 4-sulfophenyl and 4-sulfonaphthyl). Examples of the heteroaromatic group include a sulfo group and a phosphate group. Or a heterocyclic group substituted with a carboxyl group (for example, 4
-Sulfo-2-thienyl group, 4-sulfo-2-pyridyl group) and the like.

More preferred are the above-mentioned alkyl groups having a hydrocarbon aromatic ring or a heteroaromatic ring substituted with the above-mentioned sulfo group, phosphate group and / or carboxyl group, and particularly preferred are the above-mentioned sulfo group and phosphorus group. An alkyl group having a hydrocarbon aromatic ring substituted with an acid group or a carboxyl group. Most preferably, 2-sulfobenzyl, 4
-Sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 4-phenyl-4-sulfobutyl.

Formula (IV), (V), (VI) or (VII)
Is a methine dye represented by the formula (III):₁ Represented by
R represents a chromophore₁₇, R₁₈, R₁₉, R₂₀,
R_{twenty one}, R _{twenty two}, R_{twenty three}, R_{twenty four}, And R_{twenty five}And a substituent represented by
And the above-mentioned unsubstituted alkyl group and substituted alkyl
Group (eg, carboxyalkyl group, sulfoalkyl
Group, aralkyl group, aryloxyalkyl group).

Formula (IV), (V), (VI) or (VII)
Is a methine dye represented by the formula (III):_Two Represented by
R represents a chromophore₁₇, R₁₈, R₁₉, R₂₀,
R_{twenty one}, R _{twenty two}, R_{twenty three}, R_{twenty four}, And R_{twenty five}And a substituent represented by
Is preferably an unsubstituted alkyl group or a substituted alkyl group.
And more preferably an alkyl having an anionic substituent.
Kill group (for example, carboxyalkyl group, sulfoalkyl
Group), more preferably a sulfoalkyl group.
You.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
_{L 15, L 16, L 17} , L 18, L 19, L 20, L 21, L 22, L
_{23, L 24, L 25,} L 26, L 27, L 28, L 29, L 30,
_{L 31, L 32, L 33} , L 34, L 35, L 36, L 37, L 38, L
_{39, L 40, L 41,} L 42, L 43, L 44, L 45, L 46,
_{L 47, L 48, L 49} , L 50, L 51, L 52, L 53, L 54, L
_{55, L 56, L 57,} L 58, L 59, L 60, L 61, L 62,
L ₆₃ , L ₆₄ , L ₆₅ , L ₆₆ and L ₆₇ each independently represent a methine group. The methine groups represented by L _{1 to} L ₆₇ may have a substituent, and examples of the substituent include the aforementioned V. For example, a substituted or unsubstituted alkyl group having 1 to 15, preferably 1 to 10, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted carbon atom Numbers 6 to 20,
Preferably it has 6 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 aryl groups (e.g., phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms,
Preferably it has 4 to 15 carbon atoms, more preferably 6 carbon atoms.
To 10 heterocyclic groups (eg, N, N-dimethylbarbituric acid group), halogen atoms (eg, chlorine, bromine, iodine, fluorine), having 1 to 15 carbon atoms, preferably 1 carbon atom
To 10, more preferably an alkoxy group having 1 to 5 carbon atoms (for example, methoxy, ethoxy), 0 to 15 carbon atoms,
Preferably it has 2 to 10 carbon atoms, more preferably 4 carbon atoms.
To 10 amino groups (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-
Methylpiperazino), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio), 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, Preferably, an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like can be mentioned.
It may form a ring with another methine group, or Z ₁
To Z ₂₅ and R _{1 to} R ₂₅ may form a ring.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{10, L 11, L 12,} L 13, L 16, L 17, L 23, L 24,
_{L 25, L 26, L 30} , L 31, L 32, L 33, L 36, L 37, L
_{43, L 44, L 45,} L 46, L 50, L 51, L 52, L 53,
L ₅₆ , L ₅₇ , L ₆₃ and L ₆₄ are preferably unsubstituted methine groups.

N₁ , N_Two , N_Three , N_Four , N_Five , N₆ , N
₇ , N₈ , N₉ , N_Ten, N₁₁, N ₁₂, And n₁₃Each
And independently represents 0, 1, 2, 3 or 4. Preferably
0, 1, 2, 3 and more preferably 0, 1, 2.
And particularly preferably 0 and 1. n₁ , N_Two , N_Three ,
n_Four , N_Five , N₆ , N₇ , N₈ , N₉ , N_Ten, N₁₁, N
₁₂, And n₁₃Is greater than 2, the methine group is repeated
It need not be the same.

P ₁ , p ₂ , p ₃ , p ₄ , p ₅ , p ₆ , p
_{7, p 8, p 9,} p 10, p 11, p 12, p 13, p 14,
p ₁₅ and p ₁₆ each independently represent 0 or 1. Preferably it is 0.

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , and M ₆
Is included in the formula to indicate the presence of a cation or anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0]
Organic ions such as -7-undecenium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, a fluorine ion, a chloride ion or an iodine ion), or a substituted allium ion.
Sulfonic acid ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion),
Rudisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion,
2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid ion Is mentioned. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. When CO ₂ ⁻ and SO ₃ ⁻ have a hydrogen ion as a counter ion, they can be described as CO ₂ H and SO ₃ H.

M ₁ , m ₂ , m ₃ , m ₄ , m ₅ , and m ₆
Represents a number of 0 or more necessary to balance the charges, preferably a number of 0 to 4, more preferably a number of 0 to 1, and 0 when a salt is formed in the molecule. .

Next, only specific examples of the dyes used in the particularly preferred technology, which have been described in detail in the description of the embodiments of the present invention, are shown below. Of course, the present invention is not limited to these.

Specific examples of the compound represented by the general formula (I) (including the lower conceptual structure) of the present invention.

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Specific examples of the compound represented by the general formula (II) (including the lower conceptual structure) of the present invention.

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Specific examples of the compound represented by formula (III) of the present invention.

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The dye of the present invention is FM Hammer.
(FMHarmer), Heterocyclic Compounds
Cyanine soybeans and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willy and Sons
n Wiley &amp; Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry ", Chapter 18, Section 14, 482-515, John Wiley and Sons
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds" 2
nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, and the above-mentioned patents and literatures (cited for describing specific examples) and the like.

In the present invention, not only the sensitizing dye of the present invention but also other sensitizing dyes other than the present invention may be used or used in combination. Preferred examples of the dye used include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-CyanineDyes an
d Related Compounds), John Wiley &amp; Sons-New York,
London, 1964, D.M.
M. Sturmer), Heterocyclic Compounds-Special Topics in Heterocyclic
Chemistry (Heterocyclic Compounds-Special topics
in heterocyclic chemistry) ", Chapter 18, Chapter 14
, 482-515, etc. Preferred dyes are described in U.S. Pat. No. 5,994,051, pp. 32-44, and U.S. Pat. No. 5,747,236.
And sensitizing dyes represented by the general formulas described in pages 30 to 39 and specific examples. Also preferred cyanine dyes,
The general formulas of the merocyanine dye and rhodacyanine dye are described in U.S. Pat. No. 5,340,694 at columns (X) to (X).
(I), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or less)). .

One of these sensitizing dyes may be used.
Two or more sensitizing dyes may be used, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229.
No. 3,397,060 and 3,522,052
No. 3,527,641, No.3,617,293
No. 3,628,964 and 3,666,480
Nos. 3,672,898 and 3,679,428
Nos. 3,303,377 and 3,769,301
No. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1, 507, 803, JP-B-43-493
No. 36, No. 53-12375, JP-A-52-1106
No. 18, No. 52-109925 and the like.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful in spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat. No. 3,511,66.
No. 4, No. 3,615,613, No. 3,615,632
Nos. 3,615,641, 4,596,767
Nos. 4,945,038 and 4,965,182
Nos. 4,965,182 and 2,933,390
Nos. 3,635,721 and 3,743,510
Nos. 3,617,295, 3,635,721, etc., and the method described in the above-mentioned patents is preferred for the use thereof.

It has been recognized that the timing at which the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been useful. During the preparation of the emulsion. For example, U.S. Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in, for example, Japanese Patent No. 196749, the stage before silver halide grain formation step and / or before desalting, the period during and / or after desalting and before the start of chemical ripening,
As disclosed in JP-A-58-113920 and the like, any time during or immediately before chemical ripening, during a process, or after chemical ripening and before coating, the emulsion may be added at any time before the coating. May be. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or during the chemical ripening step. It may be added separately after completion, or before or after chemical ripening or during the process and after completion, and may be added by changing the kind of compound and compound combination to be added separately. May be.

The addition amount of the sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) depends on the shape and size of silver halide grains. ^Per mol of 1 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of × 10 ^{−6 to} 1.5 × 10 ⁻³ mol is more preferable. However, when the sensitizing dye of the present invention is adsorbed in multiple layers as described above, an amount necessary for the multilayer adsorption is added.

The sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. These can be first dissolved in an appropriate solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be made to coexist. Also, ultrasonic waves can be used for dissolution. As a method for adding the compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, and a method of dispersing in a water-soluble solvent and adding this dispersion to the emulsion, described in U.S. Pat. No. 3,822,135. A method of dissolving a compound in a surfactant and adding the solution to an emulsion, and dissolving using a compound that causes a red shift as described in JP-A-51-74624, and dissolving the solution in the emulsion. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid substantially free of water and the solution is added to an emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,99
Nos. 6,287, 3,429,835 and the like can also be used.

In the present invention, examples of the silver halide-adsorbing compound other than the sensitizing dye (a photographically useful compound adsorbed on silver halide grains) include an antifogging agent, a stabilizer, and a nucleating agent. Antifoggants and stabilizers are described in, for example, Research Disclosure Magazine (Research)
Disclosure) Volume 176 Item 17643
(RD17643), 187, Item 18716 (RD18716) and 308, Item 308119 (RD308119). Examples of the nucleating agent include, for example, US Pat. Nos. 2,563,785 and 2,582.
Hydrazines described in US Pat.
27,552, hydrazides, hydrazones, British Patent 1,283,835, JP-A-52-696.
13, No. 55-138742, No. 60-11837
No. 62-210451, No. 62-291637
No. 3,615,515 and 3,719,49.
4, 3,734, 738, 4,094,683, 4,115,122, 4306016, 44710
Heterocyclic quaternary salt compounds described in US Pat.
Sensitizing dyes having a substituent having a nucleating effect in a dye molecule described in US Pat. No. 4,030,9;
25, 4,031,127, 4,245,037,
4,255,511, 4,266,013, 4,
276, 364, thiourea-linked acylhydrazine-based compounds described in British Patent 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748.
Sialhydrazine-based compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole and the like as described in British Patent 2,011,391B or the like as an adsorptive group are used.

In the present invention, preferred silver halide adsorptive compounds include nitrogen-containing heterocyclic compounds such as thiazole and benzotriazole, mercapto compounds, thioether compounds, sulfinic acid compounds, thiosulfonic acid compounds, and the like.
A thioamide compound, a urea compound, a selenourea compound and a thiourea compound, particularly preferably a nitrogen-containing heterocyclic compound, a mercapto compound, a thioether compound and a thiourea compound, particularly preferably a nitrogen-containing heterocyclic compound. The nitrogen-containing heterocyclic compound has the general formula (VIII)
Nitrogen-containing heterocyclic compounds represented by formulas (XI) to (XI) are preferred.

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The compound of the general formula (VIII) is a nitrogen-containing heterocyclic compound containing an imino group (which can be interchangeably isomer) in a heterocyclic ring, and the compound of the general formula (IX) is a mercapto group (which can be interchangeably isomerized). The compound of the general formula (X) is a nitrogen-containing heterocyclic compound containing a thione group (not interchangeable isomer), and the compound of the general formula (XI) is a compound containing a quaternary ammonium group. It is a nitrogen heterocyclic compound. They may also be in the form of suitable salts. Where Q ₁ , Q ₂ , Q ₃ , Q
₄ represents a nitrogen-containing heterocyclic ring, for example, an imidazole ring, a benzimidazole ring, a naphthoimidazole ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, a benzoselenazole ring, and a triazole ring. Benzotriazole ring, tetrazole ring, azaindene ring (eg, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring), purine ring, thiadiazole ring, oxadiazole ring, selenadiazole ring, indazole ring , A triazine ring, a pyrazole ring, a pyrimidine ring, a pyridazine ring, a quinoline ring, a rhodanine ring, a thiohydantoin ring, an oxazolidinedione ring, and a phthalazine ring. Among these, in the general formula (VIII), an azaindene ring, a (benzo) triazole ring, an indazole ring, a triazine ring, a purine ring, a tetrazole ring and the like are preferable, and the general formula (IX)
In the general formula (X), there are a tetrazole ring, a triazole ring, a (benzo) imidazole ring, a (benzo) thiazole ring, a (benzo) oxazole ring, a thiadiazole ring, an azaindene ring and a pyrimidine ring. , (Benzo) imidazole ring, (benzo) oxazole ring, triazole ring, tetrazole ring and the like. In the general formula (XI), (benzo, naphtho) thiazole ring, (benzo, naphtho) imidazole ring, (benzo, naphtho) And an oxazole ring. The “(benzo, naphtho) thiazole ring” in the above display shall mean “thiazole ring, benzothiazole ring or naphthothiazole ring” (the same applies to other cases). These heterocycles may have a suitable substituent, for example, a hydroxyl group, an alkyl group (such as a methyl group, an ethyl group, or a pentyl group), an alkenyl group (such as an allyl group), and an alkylene group (such as an ethynyl group). ), Aryl group (phenyl group, naphthyl group, etc.), aralkyl group (benzyl group, etc.), amino group, hydroxyamino group, alkylamino group (ethylamino group, etc.), dialkylamino group (dimethylamino group, etc.), aryl Amino group (phenylamino group, etc.), acylamino group (acetylamino group, etc.), acyl group (acetyl group, etc.), alkylthio group (methylthio group, etc.), carboxy group, sulfo group, alkoxyl group (ethoxy group, etc.), aryloxy group (Such as a phenoxy group),
Alkoxycarbonyl group (methoxycarbonyl group, etc.), carbamoyl group which may be substituted, sulfamoyl group which may be substituted, ureido group which may be substituted, cyano group, halogen atom (such as chlorine atom and bromine atom), nitro group, mercapto group , A heterocyclic ring (such as a pyridyl group) and the like. In the formula, R represents an alkyl group (methyl group, ethyl group, hexyl group, etc.), an alkenyl group (allyl group, 2-
Butenyl group), an alkylene group (such as an ethynyl group),
Represents an aryl group (such as a phenyl group), an aralkyl group (such as a benzyl group), and the like, which may further have a suitable substituent. X ^- represents an anion (for example, an inorganic anion such as a halogen ion or an organic anion such as paratoluenesulfonate). Preferred among the above compounds are compounds of the general formulas (VIII), (IX) and (XI). Particularly preferred in the formula (VIII) are tetrazaindenes substituted with a hydroxyl group (which may have an imino group in a tautomeric isomerism). In general formula (IX), it is a mercaptotetrazole having an acidic group (carboxy group, sulfo group). In the general formula (XI), they are benzothiazoles. Among the above compounds, compounds of the general formulas (VIII) and (IX) combine with silver ions to form a silver salt, and the solubility product of the silver salt in water near room temperature is 10 ⁻⁹ to 10 ⁻⁹ . A nitrogen-containing heterocyclic compound having 10 ^-20 , especially 5 × 10 ^-10 to 10 ^-18 is preferred.

The photographic useful compound may be added before the sensitizing dye is added, after the end of the addition, or during the period from the start of the addition to the end of the addition. This is the period before the addition of the dye and from the start to the end of the addition, and more preferably the period from the start to the end of the addition of the sensitizing dye. The addition amount of the photographically useful compound varies depending on the function of the additive and the type of emulsion, but typically,
It is 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol / mol Ag.

Next, specific examples of the photographically useful compound which is adsorbable to particles will be shown. Of course, the present invention is not limited to these.

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In the present invention, the photographic emulsion controlling the light-sensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, particularly preferably 5 mol% or more, a stronger multilayer adsorption structure can be constructed. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion have regular crystals such as cubic, octahedral, tetradecahedral, and rhomboid dodecahedron, and irregular grains such as spherical and tabular. It may be one having an (irregular) crystal form, one having a higher-order plane ((hkl) plane), or a mixture of grains of these crystal forms. The particles are described in detail below. See Journal of Imagi for particles with higher planes.
ng Science, 30 (1986), pages 247 to 254. Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains singly or as a mixture of two or more. The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. May consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

In the present invention, tabular silver halide grains having a silver halide composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver iodochloride are preferably used. The tabular grains preferably have a main surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. The hexagonal monodispersed flat plate is described in Japanese Patent Publication No. 5-61205.

Tabular grains having a (100) plane as a main surface,
Hereinafter, the (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent side ratio of less than 5: 1 are called tabular grains. In silver chloride or tabular grains containing a large amount of silver chloride, the (100) tabular grains originally have higher stability on the main surface than the (111) tabular grains. In the case of a (111) flat plate, it is necessary to stabilize the (111) main surface.
-80660, JP-A-9-80656 and U.S. Pat. No. 5,298,388.

The silver chloride or the (111) flat plate having a high silver chloride content used in the present invention is disclosed in the following patents. U.S. Patent No. 4,414,306, U.S. Patent No. 4,400,463, U.S. Patent No. 4,713,323
No. 4,783,398; U.S. Pat.
No. 491, U.S. Pat. No. 4,983,508, U.S. Pat.
No. 804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The high silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
U.S. Pat. No. 4,443,426; U.S. Pat. No. 4,439,520
No. 4,414,310; U.S. Pat.
048, U.S. Pat. No. 4,647,528, U.S. Pat.
No. 665012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat.
6, U.S. Pat. No. 4,722,886, U.S. Pat.
No. 5617, U.S. Pat. No. 4,755,456, U.S. Pat. No. 4,806,461, U.S. Pat. No. 4,801,522, U.S. Pat. No. 4,835,322, U.S. Pat.
U.S. Pat. No. 4,914,014, U.S. Pat.
5, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 5,350, U.S. Pat. No. 5,061,609, U.S. Pat. No. 5,061,616, U.S. Pat. No. 5,068,173, U.S. Pat. No. 5,132,203, U.S. Pat.
No. 5,334,469, U.S. Pat.
No. 495, US Pat. No. 5,358,840, US Pat.
372927.

The (100) flat plate used in the present invention is described in the following patents. US Patent No. 43
No. 86156, US Pat. No. 5,275,930, US Pat. No. 5,292,632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635.
No. 5,356,764, European Patent No. 5699.
No. 71, EP 737887, JP-A-6-308
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and grains having an aspect ratio of 2 or more (preferably 100 or less), preferably 5 or more and 80 or less, more preferably 8 or more and 80 or less represent 50% of all silver halide grains ( (Area)) is preferred. The thickness of the tabular grains is preferably less than 0.2 μm, more preferably less than 0.1 μm, even more preferably less than 0.07 μm. The following technology is applied to prepare such high aspect ratio and thin tabular grains. The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. The emulsion of the present invention contains 1 emulsion per grain.
Silver halide grains containing 0 or more dislocation lines account for 1% of all grains.
It preferably occupies 00 to 50% (number), more preferably 100 to 70%, and particularly preferably 1 to 50%.
It accounts for 00 to 90%.

If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when obtaining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part or only the shell part of the grain can be selected. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals can be added in the form of ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, or salts that can be dissolved at the time of particle formation, such as six-coordinate complex salts and four-coordinate complex salts. For example,
CdBr ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO
₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl
₆ , (NH ₄ ) ₃ RhCl ₆ and K ₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. A water-soluble silver salt (eg, AgNO ₃ ) or an aqueous alkali halide solution (eg, NaCl, KB)
r, KI) and can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of the production process of a silver halide emulsion. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred. One of the chemical sensitizations that can be preferably performed in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan. Published by the company
1977, (TH James, The Theo)
ry of the Photographic Pr
ocess, 4th ed, Macmillan, 19
77) can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, 6 June 1975.
Moon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_Two PdCl_Four , (NH_Four)_Two 
PdCl₆ , Na_Two PdCl_Four , (NH_Four)_Two PdCl
_Four , Li_Two PdCl_Four , Na_Two PdCl₆ Or K_Two P
dBr _Four Is preferred. Gold and palladium compounds
Is used in combination with thiocyanate or selenocyanate
Is preferred. Hypo and thiourea as sulfur sensitizers
Compound, rhodanine compound and US Patent No. 3,853
No. 7,711, No. 4,266,018 and No.
Sulfur-containing compounds described in 4,054,457
Can be used. In the presence of so-called chemical sensitization aid
Can also be chemically sensitized. Useful chemical sensitizer
For azaindene, azapyridazine and azapyrimidine
Fog in the process of chemical sensitization
Compounds known to be augmented are used. Chemistry
Examples of sensitizing aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
No. 7, JP-A-58-126526 and the aforementioned duffin
"Photographic Emulsion Chemistry", pages 138-143.
You. The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of the gold sensitizer is 1 per mole of silver halide.
× 10^-Four~ 1 × 10^-7Mole, more preferably
1 × 10^-Five~ 5 × 10^-7Is a mole. Palladium compound
Is preferably 1 × 10^-3From 5 × 10^-7It is. H
Preferred of ocyan compound or selenocyan compound
The range is 5 × 10^-2From 1 × 10^-6It is. Halo of the present invention
The preferred amount of sulfur sensitizer to be used for silver gemide grains is
1 × 10 per mole of silver halide^-Four~ 1 × 10^-7In mole
Yes, more preferably 1 × 10^-Five~ 5 × 10^-7Mole
It is. A preferred sensitizing method for the emulsion of the present invention is
There is Len sensitization. Known instability in selenium sensitization
Using a selenium compound, specifically, a colloidal metal
, Selenoureas (eg, N, N-dimethylselene)
Nourea, N, N-diethylselenourea), selenoketone
Use of selenium compounds such as selenium and selenoamides
Can be. Selenium sensitization is sulfur sensitization or precious metal sensitization
Or it is better to use in combination with both.
is there.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in an atmosphere of a low pAg of pAg 1 to 7 called silver ripening, and a method of pH 8 to ripening called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted. Examples of the reduction sensitizer include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Alternatively, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a water-insoluble silver salt such as silver halide, silver sulfide or silver selenide, or a water-soluble silver salt such as silver nitrate. May be formed. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, for example, ozone, hydrogen peroxide and its adduct (eg, NaBO ₂
・ H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salt (for example, K ₂ S ₂ O)
₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂
O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂
O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O),
Oxygenates such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, and perhalates (eg, periodate) Potassium), salts of higher valent metals (eg, potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain a compound other than the above-mentioned silver halide-adsorbing compound for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can also be contained. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a support, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. It is sufficient that at least one layer is provided, and there is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, a unit photosensitive layer is generally used. The sequence of the red-sensitive layer in order from the support side,
A green color sensitive layer and a blue color sensitive layer are provided in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

A non-light-sensitive layer such as an intermediate layer of each layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers and DIR compounds as described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of an emulsion layer can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / R
H / RL, or BH / BL / GH / GL / RL /
They can be installed in the order of RH.

As described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, a blue-sensitive layer / GL / RL / GH / RH can be provided in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a lower sensitivity than the middle layer. Further, there is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202264, a medium-speed emulsion layer / They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column to 996, right to 998 right Super strong Sensitizer Page 649 Right column 4 Brightener 24 Page 647 Page Right column 998 Right 5 Antifoggant, Page 24 to 25 Page 649 Right column 998 Right to 1000 Right and Stabilizer 6 Light absorber, 25 to 26 649 Page right column to 1003 left to 1003 right Filter dye, page 650 Left column UV absorber 7 Stain inhibitor page 25 right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 Page left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant 27 page 650 Page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left 1006 left Surfactant 13 Static Page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left Also to prevent deterioration of photographic performance due to formaldehyde gas For this purpose, it is preferable to add a compound which can react with formaldehyde described in U.S. Pat.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. US Pat.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO 88/04795 are particularly preferred.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and European Patent 341,188A.
No.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and the same No. 307105, VII-
Patents described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012.

Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent No. 2,092.
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950 and JP-A-62-24252.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A , RD. No. 1
Bleaching accelerator releasing couplers described in US Pat. Nos. 4,5, 1449, 24241, and JP-A-61-201247.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, and couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181. .

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-tert-amylphenyl)
Phthalates, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2-ethylhexyl benzoate) , Dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate); amides (for example, N, N-diethyldodecaneamide, N,
N-diethyl laurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis (2- Ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-)
5-tert-octylaniline); and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or less can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described, for example, in US Pat.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-63-257747, may be used.
272248 and JP-A-1-80941, for example, 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, −
It is preferable to add various preservatives or fungicides such as phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. For example, general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers can be mentioned as typical examples. The present invention can be particularly preferably used for a color duplication film.

Suitable supports that can be used in the present invention are described in, for example, RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T1 / 2 is preferably 30 seconds or less,
0 second or less is more preferable. The film thickness here means the film thickness measured under humidity control at 25 ° C. and 55% relative humidity (2 days).
Also, the film swelling rate T1 / 2 can be measured according to techniques known in the art, for example, by A. Green et al., Photographic Science and Engineering (Photo).
gr. Sci. Eng. ), Vol. 19, No. 2, 124-1
It can be measured by using a serometer (swelling meter) of the type described on page 29. T1 / 2 is defined as 90% of the maximum swollen film thickness reached when the film is processed at 30 ° C. for 3 minutes and 15 seconds with a color developing solution, and defined as the time required to reach 1/2 of the saturated film thickness. I do.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-
Sulfates of amino-N-ethyl-N-β-hydroxyethylaniline are preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution may be, for example, a pH buffer such as an alkali metal carbonate, borate or phosphate,
It generally contains a development inhibitor or antifoggant such as chloride, bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine and catecholsulfonic acid; ethylene glycol; Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos Various chelating agents such as carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-
Known black and white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. The p of these color developing solutions and black-and-white developing solutions
H is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the processing liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [capacity of processing solution (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.1% or less. 001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. And a slit developing method described in JP-A-63-216050. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, by using means for suppressing the accumulation of bromide ions in the developer, the replenishing amount can be reduced.

The time for the color development processing is usually set to 2 to 5 minutes. However, the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. .

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fix processing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids (particularly, sodium persulfate is suitable for a color negative film for movies), quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Can be used. Of these, iron (III) aminopolycarboxylate complexes, including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminoboric acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: for example, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95731, No. 53-
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. 17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A-51-140129; thiazolidine derivatives described in JP-A-51-140129; Japanese Patent Publication No. 45-8506;
Nos. 832 and 53-32735, U.S. Pat.
No. 6,561, the thiourea derivative described in West German Patent 1,
127,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,741
8,430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40943 and JP-A-49-59644.
Nos. 53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Of these, use of thiosulfates is common, and in particular, ammonium thiosulfate can be used most widely. Also, thiosulfate and, for example, thiocyanate,
A combination use of a thioether compound and thiourea is also preferable. Examples of the preservatives of the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and European Patent No. 2
Sulfinic acid compounds described in No. 94,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl for adjusting pH. It is preferable to add imidazoles such as imidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering step is preferably as short as possible without causing desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that stirring is strengthened as much as possible. As a specific method for enhancing the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method described in JP-A-62-183461, using a rotating means. There is a method to improve the effect. In addition, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the turbulence of the emulsion surface is used to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. There is a method to make it. Such an agitation improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, thereby increasing the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect by the bleaching accelerator.

The automatic developing machine used for developing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of water to be washed in the water washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use,
Further, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to a replenishment method such as countercurrent or forward flow, and other various conditions. Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is shown in Journal of
the Society of Motion Pi
cure and Television Engi
neers, vol. 64, p. 248-253 (1955)
May issue).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, there is a problem that bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also described in JP-A-57-8542, for example, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Hiroshi Horiguchi "The Chemistry of Bactericidal and Fungicides" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Techniques" (1982) Industrial Technology Association, Japan Bactericidal and Fungicide Society, Ed. A fungicide described in "A fungus encyclopedia" (1986) can also be used.

The washing water p in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and use of the photosensitive material, but are generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

In some cases, a stabilization treatment may be further performed after the water washing treatment. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic developing machine,
When each of the above-mentioned treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color photographic light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, for example, U.S. Pat. No. 3,342,599, Research Disclosure No. 14, 850 and the same No.
Nos. 15, 15 and 159; 1
Aldol compounds described in U.S. Pat.
No. 719,492, a metal salt complex disclosed in JP-A-53-1
The urethane compounds described in JP-A-35628 can be exemplified.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

The various processing solutions in the present invention may be used at a temperature of 10 ° C. to 5
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention comprises
U.S. Pat. No. 4,500,626, JP-A-60-133
No. 449, No. 59-218443, No. 61-2380
No. 56, EP 210,660 A2 and the like.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-B-2-32615 and JP-B-3-397.
In the case where the invention is applied to a film unit with a lens described in No. 84 or the like, the effect is more easily exhibited and is effective.

The present invention can be preferably used for a diffusion transfer photographic material. The most typical form of the diffusion transfer photosensitive material is a color diffusion transfer film unit, and the typical form is such that an image receiving element and a photosensitive element are laminated on one transparent support, and the transferred image is formed. After completion of the above, there is no need to peel the photosensitive element from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer A combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye image-forming compound in each of the above emulsion layers; The magenta dye image-forming compound and the cyan dye image-forming compound are respectively combined (here, the term “infrared-sensitive emulsion layer” means 700 nm or more, especially 74 nm).
An emulsion layer having a spectral sensitivity maximum with respect to light of 0 nm or more). A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the dye image forming compound-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the developing process can be completed in a light place. If desired, a release layer may be provided at an appropriate position so that all or a part of the photosensitive element can be peeled from the image receiving element. Such an embodiment is disclosed in, for example,
67840 and Canadian Patent 674,082.

Further, as another embodiment of a laminating type, which is peeled off, at least (a) a layer having a neutralizing function, (b) a dye image receiving layer, c) a release layer, (d) a photosensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming compound, an alkali treatment composition containing a light-blocking agent, and a transparent cover sheet, wherein There is a color diffusion transfer photographic film unit having a layer having a light-shielding function on the side opposite to the side where the processing composition is developed.

In another mode in which peeling is unnecessary, the above-described photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. .
An image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and an embodiment in which the photosensitive element is intentionally peeled from the image receiving element is described in US Pat. No. 3,730,71.
No. 8 is described.

On the other hand, there are roughly two typical forms in which a photosensitive element and an image receiving element are separately coated on two supports, respectively, one of which is a peeling type, and the other is a peeling-free type. is there. More specifically, in a preferred embodiment of the peelable film unit, at least one image-receiving layer is coated on one support, and the photosensitive element is coated on a support having a light-shielding layer. Before the end of the exposure, the coated surface of the photosensitive layer and the coated surface of the mordant layer do not face each other, but after the end of the exposure (for example, during the developing process), the coated surface of the photosensitive layer is inverted in the image forming apparatus and is in contact with the coated surface of the image receiving layer. It is devised as follows. After the transfer image is completed in the mordant layer, the photosensitive element is immediately separated from the image receiving element.

In a preferred embodiment of the peeling-free film unit, at least one mordant layer is provided on a transparent support, and a photosensitive element is provided on a support having a transparent or light-shielding layer. The surface on which the photosensitive layer is applied and the surface on which the mordant layer is applied face each other.

A pressure-rupturable container (processing element) further containing an alkaline processing liquid may be combined with the above-described embodiment. In particular, in a peeling-free film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. In the case where the photosensitive element and the image receiving element are separately coated on the two supports, it is preferable that the processing element is arranged between the photosensitive element and the image receiving element at the latest at the time of development processing. The processing element preferably contains one or both of a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the film unit of the color diffusion transfer system, it is preferable that a neutralization timing mechanism composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

The dye image-forming substance used in the present invention is a non-diffusible compound which releases a diffusible dye (may be a dye precursor) in connection with silver development, or a substance which changes its own diffusivity. And the 4th of The Theory of the Photographic Process
It is stated in the edition. All of these compounds can be represented by the following general formula (XII). Formula (XII) (DYE-Y) n-ZＺDYE represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a mere bond or a linking group,
Z is related to silver development (specifically, corresponding to or inversely corresponding to a photosensitive silver salt having an image-like latent image) (DYE-Y)
causing a difference in the diffusivity of the compound represented by n-Z,
Alternatively, DYE is released, and the released DYE and (DYE-
Y) represents a group having a property that causes a difference in diffusivity with n-Z, n represents 1 or 2, and n represents 2
At this time, the two DYE-Ys may be the same or different.機能 By the function of Z, the compound is roughly classified into a negative type compound which becomes diffusible in a silver developed portion and a positive type compound which becomes diffusible in an undeveloped portion. Specific examples of the negative type Z include those which oxidize as a result of development and are cleaved to release a diffusible dye.
Specific examples of Z are described in U.S. Pat. Nos. 3,928,312 and 3,9
Nos. 93,638, 4,076,529 and 4,15
No. 2,153, No. 4,055,428, No. 4,05
No. 3,312, No. 4,198,235, No. 4,17
9,291, 4,149,892 and 3,84
4,785, 3,443,943, 3,75
No. 1,406, No. 3,443,939, No. 3,44
No. 3,940, No. 3,628,952, No. 3,98
0,479, 4,183,753, 4,14
Nos. 2,891, 4,278,750, 4,13
9,379, 4,218,368, 3,42
1,964, 4,199,355, 4,19
9,354, 4,135,929, 4,33
6,322,4,139,389,
No. 50736, No. 51-104343, No. 54-13
No. 0122, No. 53-110827, No. 56-126
No. 42, No. 56-16131, No. 57-4043,
No. 57-650, No. 57-20735, No. 53-6
Nos. 9033, 54-130927, 56-164
342, 57-119345 and the like.
Of the Z of the negative dye-releasing redox compound, a particularly preferred group is an N-substituted sulfamoyl group (an example of the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). The representative groups of Z are exemplified below, but are not limited thereto.

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For the positive type compounds, see Angev. Chem. Int. Ed. Engl., 22, 191.
(1982). Specific examples include compounds (dye developing agents) which are initially diffusible under alkaline conditions but are oxidized by development to become non-diffusible. Z useful in this type of compound is disclosed in US Pat.
No. 3606 is representative. Another type is a type which releases a diffusible dye by, for example, self-ring closure under alkaline conditions, but substantially does not release the dye when oxidized during development. For a specific example of Z having such a function, see US Pat.
980,479, JP-A-53-69033, 54
No. 130927, U.S. Pat. Nos. 3,421,964 and 4,199,355. Another type does not release the dye itself, but releases the dye when reduced. Compounds of this type can be used in combination with an electron donor to release the diffusible dye imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. For atomic groups having such a function, see, for example, US Pat. No. 4,183,75.
No. 3, No. 4, 142, 891, No. 4, 278, 750
Nos. 4,139,379 and 4,218,368
JP-A-53-110827, U.S. Pat.
8,750, 4,356,249, 4,35
8,535, JP-A-53-110827, and 54-
130927, 56-164342, published technical report 8
No. 7-6199, European Patent Publication No. 220746A2, and the like. Specific examples of Z will be described below, but the present invention is not limited thereto.

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When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron-donating compound (known as an ED compound) or a precursor (precursor) thereof. Examples of ED compounds include, for example, US Pat.
Nos. 63,393 and 4,278,750;
No. 138736. Specific examples of other types of dye image-forming substances include the following.

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The details are described in US Pat. Nos. 3,719,489 and 4,098,783. On the other hand, specific examples of the dye represented by DYE in the above general formula are described in the following documents. Examples of yellow dyes: U.S. Pat. Nos. 3,597,200, 3,309,199, 4,013,633, 4,245,028, 4,156,609 and 4,139. , 383, 4,195,992, 4,148,641, 4,148,643 and 4,336,322: JP-A-51-114930,
No. 56-71072: Research Disclosure 1763
No. 0 (1978) and No. 16475 (1977). Examples of magenta dyes: U.S. Pat. Nos. 3,453,107, 3,544,545, 3,932,380, 3,931,144, 3,932,308, and 3,954 No. 4,476, No. 4,233,237, No. 4,255,509, No. 4,250,246, No. 4,142,891, No. 4,207,104, No. 4,287,292 No .: JP-A-52-106,727
Nos. 53-23,628 and 55-36,804
No. 56-73,057, No. 56-71060,
No. 55-134. Examples of cyan dyes: U.S. Pat. Nos. 3,482,972, 3,929,760, 4,013,635, 4,268,625, 4,171,220 and 4,242 4,435,891,4,195,994,4,147,544,4,148,642; British Patent 1,551,138
Nos .: JP-A-54-99431 and JP-A-52-8827,
Nos. 53-47823, 53-143323, 5
4-99431 and 56-71061; European Patents (EP) 53,037 and 53,040; Rese
Arch Disclosure 17,630 (1978) and 16,475 (1977). These compounds are described in JP-A-62-215272, 14
It can be dispersed by the method described on pages 4-146. These dispersions are described in JP-A-62-215,272.
No. 137-144.

[0264]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of seed emulsion a) 0.017 g of KBr, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 48 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. After an aqueous KBr solution was added to adjust the silver potential to −66 mV, the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
The pAg was adjusted to 8, and a seed emulsion was prepared. This seed emulsion contains 1 mol of Ag and 8 gelatin per kg of emulsion.
0 g, tabular grains having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of core) 134 g of the above seed emulsion a was prepared.
Succinated KBr 1.9 g, average molecular weight 100000
Keep 1200 ml of aqueous solution containing 22 g of rat at 75 ° C
Stirred. AgNO _Three (43.9 g) aqueous solution and KBr water
Solution and an aqueous gelatin solution having a molecular weight of 20,000
-43570 Magnetic coupling induction type stirrer
25 minutes mixing just before addition in another chamber with
Added over time. At this time, the silver potential is changed to a saturated calomel electrode.
-40 mV.

(Formation of First Shell) After the formation of the core particles, an aqueous solution of AgNO ₃ (43.9 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber in the same manner as above, and then mixed. Added over minutes. At this time, the silver potential was set to −40 with respect to the saturated calomel electrode.
mV.

(Formation of Second Shell) After the formation of the first shell, an aqueous solution of AgNO ₃ (42.6 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber of the same type. Added over 17 minutes. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Thereafter, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to −55 mV, and AgNO ₃ (7.
1 g) aqueous solution, KI (6.9 g) aqueous solution and molecular weight 200
The gelatin aqueous solution of No. 00 was mixed immediately before the addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential is set at 30 with respect to the saturated calomel electrode.
mV. Perform normal water washing, add gelatin,
PH was adjusted to 5.8 and pAg to 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b had an average equivalent circle diameter of 3.3 μm,
Coefficient of variation of equivalent circle diameter 21%, average thickness 0.090μm,
The tabular grains had an average aspect ratio of 37. Further, 70% or more of the total projected area has a circle equivalent diameter of 3.3 μ or more and a thickness of 0.3 μm.
Occupied by tabular grains of 090 μm or less. When the dye occupied area is 80 色素² , the one-layer saturation coverage is 1.4.
It was 5 × 10 ⁻³ mol / mol Ag.

Comparative Example 1 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ^-4 mol / mol Ag was added and stirred for 60 minutes. Comparative Example 2 Chemical sensitization was performed in the same manner as in Comparative Example 1, except that D-2 was used instead of D-1 and D-3 was used instead of D-4. Comparative Example 3 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ⁻⁴ mol / mol Ag was added thereto and stirred for 10 minutes. Thereafter, D-20 was added at 2.0 × 10 ⁻³ mol /
molAg was added and the mixture was further stirred for 60 minutes. Invention 1 Emulsion b was heated to 56 ° C., and D-2 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-3 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ⁻⁴ mol / mol Ag was added thereto and stirred for 10 minutes. Thereafter, D-20 was added at 2.0 × 10 ⁻³ mol /
molAg was added and the mixture was further stirred for 60 minutes. However, the sensitizing dye was used as a solid fine dispersion prepared by the method described in JP-A-11-52507. That is, 0.8 parts by weight of sodium nitrate and 3.2 parts by weight of sodium sulfate are dissolved in 43 parts of ion-exchanged water, and 13 parts by weight of a sensitizing dye are added.
By dispersing at 20 rpm for 20 minutes, a solid dispersion of the sensitizing dye was obtained.

The measurement of the light absorption intensity per unit area is
Apply the thin emulsion to a glass slide
Using Ice Microscope MSP65
The transmission spectrum and the reflection of each particle are
The emission spectrum was measured to determine the absorption spectrum. Transparent
The hyperspectral reference is the particle-free part
And the reflection spectrum is a silicon camera whose reflectance is known.
The carbide was measured and used as a reference. Measurement part is diameter
1μm circular aperture, with aperture on particle outline
Adjust the position so that the char section does not overlap and 14000
cm^-1(714 nm) to 28000 cm^-1(357n
Transmission spectrum and reflection spectrum in the wave number range up to m)
1-T (transmittance) -R (reflectance)
The absorption spectrum was determined as A. Silver halide absorption
Is subtracted to obtain an absorption rate A ′, and −Log (1-A ′) is
Wave number (cm^-1), Halving the integrated value
The light absorption intensity per surface area was used. Integration range is 1400
0cm^-1From 28000cm ^-1Up to. At this time,
The source is a tungsten lamp and the light source voltage is 8V
Was. Primary to minimize dye damage from light irradiation
Using the monochromator on the side, the wavelength interval is 2 nm,
The cut width was set to 2.5 nm. Absorb about 200 particles
The light absorption intensity and light absorption intensity.
Coefficient of variation between particles at wavelength intervals showing 50% of Amax
I asked. Also, from the maximum absorption wavelength of each particle,
The percentage of particles that are frequently included in the 10 nm wavelength range
I asked.

A gelatin hardener and a coating aid were added to the obtained emulsion, and a gelatin protective layer was coated on a cellulose acetate film support so that the coated silver amount was 3.0 g-Ag / m ^2. At the same time. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter.
Using a Fuji gelatin filter SC-50 (manufactured by FUJIFILM Corporation) for minus blue exposure which excites the dye side as a color filter, light of 500 nm or less was blocked and the sample was irradiated. The exposed sample was the following surface developer MAA
Developed at -20 ° C. for 10 minutes.

Surface developer MAA-1 formulation Metol 2.5 g L-ascorbic acid 10 g Navox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water was added to add 1 liter pH 9.8

After development, fixing was performed at 20 ° C. with the following fixing solution. Fixing solution formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Water added 1 liter The processed film was measured for optical density by Fuji automatic densitometer The sensitivity was represented by the reciprocal of the amount of light required to provide an optical density of +0.2, and the sensitivity of Comparative Example 1 was expressed as 100. The gradation is represented by the reciprocal of the ratio of the amount of light required to give a density difference of fog +0.2 to fog +1.2, and the gradation of Comparative Example 1 is represented as 100. The results are shown in Table 1.

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[Table 1]

It has been clarified that in the multilayer adsorption system, by making the adsorption state of the sensitizing dye uniform among the particles, it is possible to achieve higher sensitivity in comparison with the conventional multilayer adsorption system.

Example 2 Silver halide emulsions A-1 to A-4,
BP were prepared. (Production Method of Emulsions A-1 to A-4) 31.7 phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000.
42.2 L of an aqueous solution containing 31.7 g of KBr and KBr at 35 ° C.
And stirred vigorously. 1583 ml of an aqueous solution containing 316.7 g of AgNO ₃ and 1583 ml of an aqueous solution containing 52.7 g of low molecular weight gelatin having a molecular weight of 15,000 and 221.5 g of KBr were added over 1 minute by the double jet method. Immediately after the addition is completed, 52.8 g of KBr is added, and A is added.
2485 ml of an aqueous solution containing 398.2 g of gNO ₃ and K
2581 ml of an aqueous solution containing 291.1 g of Br was added over 2 minutes by the double jet method. Immediately after the addition was completed, 47.8 g of KBr was added. Thereafter, the temperature was raised to 40 ° C. and the product was aged sufficiently. After completion of ripening, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 79.2 g of KBr were added, and 5103 g of AgNO ₃ was added.
And an aqueous KBr solution were added over a period of 12 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 1.4 times the initial flow rate. At this time, the silver potential was kept at -60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added, pH, 5.7, pAg, 8.
8. A seed emulsion was prepared by adjusting the weight in terms of silver per kg of the emulsion to 131.8 g and the gelatin weight to 64.1 g. 46 g of phthalated gelatin having a phthalation rate of 97%, 1.7 g of KBr
Was maintained at 75 ° C. and stirred vigorously. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (L7602 manufactured by Nippon Unicar Co., Ltd.) was added. 5.5 pH by the addition of H ₂ SO ₄
And adjusted to an aqueous solution 6 containing 7.0 g of AgNO ₃ .
7.6 ml of the KBr aqueous solution was added over 6 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate. At this time, the silver potential was kept at -20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO ₃ and 13 were added to a stirring device installed outside the reaction vessel.
An aqueous solution containing 4.4 g, 762 ml and KBr 90.1 g
And 762 ml of an aqueous solution containing 9.46 g of KI and 38.1 g of gelatin having a molecular weight of 20,000 were simultaneously added to prepare an AgBrI fine grain emulsion (average size: 0.015 μm) having a silver iodide content of 7 mol%, and this AgBrI was placed in a reaction vessel. The emulsion was added over 90 minutes. At this time,
The silver potential was kept at -30 mV with respect to the saturated calomel electrode. 121.3 m of an aqueous solution containing 45.6 g of AgNO ₃
and KBr aqueous solution were added by a double jet method over 22 minutes. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was raised to 82 ° C. and KBr was added to adjust the silver potential to −80 mV, the AgI fine grain emulsion having a grain size of 0.037 μm was converted to 6.3 in terms of KI weight.
3 g were added. Immediately after the addition is completed, AgNO ₃ , 6
206.2 ml of an aqueous solution containing 6.4 g were added over 16 minutes. During the initial 5 minutes of the addition, the silver potential was kept at -80 mV with an aqueous KBr solution. After washing with water, add gelatin and add 4
The pH was adjusted to 5.8, pAg, 8.7 at 0 ° C. . After adding compounds 11 and 12, the temperature was raised to 60 ° C. Emulsion A-1 After adding 4.50 × 10 ⁻⁴ mol / mol Ag of D-14, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were optimally added. Chemical sensitization was applied. Further, D-14 is increased by 0.5
1 × 10 ⁻⁴ mol / mol Ag was added and stirred for 60 minutes. Emulsion A-2 Chemical sensitization was performed in the same manner as Emulsion A-1, except that D-15 was used instead of D-14. Emulsion A-3 After adding 4.50 × 10 ⁻⁴ mol / mol Ag of D-14, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were optimally added. Chemical sensitization was applied. Further, D-14 is increased by 0.5
1 × 10 ⁻⁴ mol / mol Ag was added and stirred for 10 minutes. Thereafter, 1.02 × 10 ⁻³ mol of D-20 was added, and the mixture was further stirred for 60 minutes. Emulsion A-4 After adding 4.50 × 10 ⁻⁴ mol / mol Ag of D-15, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were optimally added. Chemical sensitization was applied. Further, D-15 is increased by 0.5
1 × 10 ⁻⁴ mol / mol Ag was added and stirred for 10 minutes. Thereafter, 1.02 × 10 ⁻³ mol of D-20 was added, and the mixture was further stirred for 60 minutes. However, sensitizing dyes are disclosed in
It was used as a solid fine dispersion prepared by the method described in No. 1-52507. That is, 0.8 parts by weight of sodium nitrate and 3.2 parts by weight of sodium sulfate
Dissolve in 3 parts, add 13 parts by weight of sensitizing dye,
A dispersion of the sensitizing dye was obtained by dispersing the mixture at 2000 rpm for 20 minutes using a dissolver blade under the above conditions.

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[0281] The obtained particles were cooled with liquid nitrogen while passing through.
Observed with a per-electron microscope, the projected area from the particle center
In 99.8% of the particles had no dislocations within 80%.
%Were present. In addition, 20% of the projected area from the outer periphery of the particle
An average of 12 dislocation lines per particle are observed around the particle
Was done. (Preparation of Emulsion B) (Emulsion for low-sensitivity blue-sensitive layer) Including 0.96 g of low molecular weight gelatin, 0.9 g of KBr
1192 ml of the aqueous solution was kept at 40 ° C. and stirred vigorously.
AgNO_Three 37.5 ml of an aqueous solution containing 1.49 g and K
Double-jet 37.5 ml of an aqueous solution containing 1.5 g of Br.
The method was added over 30 seconds. Add 1.2g KBr
After that, the temperature was raised to 75 ° C. to ripen. After aging sufficiently,
Mino group chemically modified with trimellitic acid, molecular weight 1000
Add 30 g of trimellitized gelatin of 00, pH
Was adjusted to 7. 6 mg of thiourea dioxide were added. A
gNO_Three , 116ml aqueous solution containing 29g and KBr aqueous solution
The final flow rate of the liquid is double the initial flow rate by the double jet method.
Was added at an accelerated flow rate. At this time, the silver potential is saturated
It was kept at -20 mV with respect to the calomel electrode. AgN
O _Three440.6 ml of an aqueous solution containing 110.2 g and KB
The final flow rate of the aqueous solution is doubled by the double jet method.
Accelerate the flow rate to 5.1 times and add over 30 minutes
did. At this time, AgI fine grains used in the preparation of Emulsion A-1
The emulsion was adjusted so that the silver iodide content was 15.8 mol%.
At the same time, and add silver potential to saturated calorie
The voltage was maintained at 0 mV with respect to the electrode. AgNO_Three , 24.1
g in an aqueous solution containing 96.5 ml of KBr and KBr aqueous solution.
It was added over 3 minutes by the wet method. At this time, the silver potential is set to 0
mV. Sodium ethylthiosulfonate, 26
mg was added, and the temperature was lowered to 55 ° C., and an aqueous KBr solution was added.
The silver potential was adjusted to -90 mV. AgI fine mentioned above
8.5 g of the grain emulsion was added in terms of KI weight. End of addition
Later, AgNO_Three 228 ml of an aqueous solution containing 57 g
Was added over 5 minutes. At this time, the potential at the end of the addition is
It adjusted with KBr aqueous solution so that it might become +20 mV. Sensitization
After the addition of dyes 11 and 12, potassium thiocyanate is added.
, Chloroauric acid, sodium thiosulfate, N, N-dimethyl
Luselenourea was added for optimal chemical sensitization. Chemical sensitization
At the end, compound 13 and compound 14 were added. here
Optimum chemical sensitization refers to the sensitizing dye and each compound.
Product per 10 mol of silver halide ^-1From 10^-8
It means that it was selected from the range of addition amount of mol.

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(Preparation of Emulsion C) (Emulsion for low-sensitivity blue-sensitive layer) An aqueous solution containing 35 μmol of methionine per gram, 1.02 g of phthalated gelatin having a molecular weight of 100,000, phthalated gelatin having a phthalation rate of 97%, and 0.97 g of KBr was 1192 m.
1 was kept at 35 ° C. and stirred vigorously. AgNO ₃ , 4.
42 ml of an aqueous solution containing 47 g and 42 ml of an aqueous solution containing 3.16 g of KBr were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C., and the mixture was sufficiently aged. After ripening, trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B 4
1.2 g and 18.5 g of NaCl were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. 203 ml of an aqueous solution containing 26 g of AgNO ₃
And an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. AgN
440.6 ml of an aqueous solution containing 110.2 g of O ₃ and KB
The r aqueous solution was added over a period of 24 minutes by a double jet method at an accelerated flow rate such that the final flow rate was 5.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion A-1 was simultaneously added at an accelerated flow rate such that the silver iodide content became 2.3 mol%, and the silver potential was -20 mV with respect to the saturated calomel electrode. Kept. After adding 10.7 ml of 1N aqueous potassium thiocyanate solution, AgNO
₃ , 153.5 ml of an aqueous solution containing 24.1 g and an aqueous KBr solution were added over 2 minutes and 30 seconds by a double jet method. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. A mentioned above
6.4 g of the gI fine grain emulsion was added in terms of KI weight. Immediately after the addition, an aqueous solution 40 containing 57 g of AgNO ₃
4 ml was added over 45 minutes. At this time, it was adjusted with an aqueous KBr solution so that the potential at the end of the addition was -30 mV. It was washed with water and chemically sensitized almost in the same manner as Em-B. It was changed to 2.0 times the AgNO ₃ addition amount during nucleation in the preparation of (Emulsion preparation of D) (low sensitivity blue-sensitive layer emulsion) Em-C. And the final AgNO ₃ , 57
g at the end of addition of 404 ml of an aqueous solution containing
It changed so that it might adjust with KBr aqueous solution so that it might be set to mV. Except for this, it was prepared in substantially the same manner as in Em-C. (Preparation of Emulsion E) (Magenta color-forming layer having a spectral sensitivity peak at 480 to 550 nm) (Layer giving a multilayer effect to red-sensitive layer) Low molecular weight gelatin having a molecular weight of 15,000, 0.71 g, KBr, 0.92 g,
Modified silicone oil 0.2 used in the preparation of Emulsion A-1
g of an aqueous solution containing g was maintained at 39 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. AgNO ₃ , 0.45
g and an aqueous solution of KBr containing 1.5 mol% of KI were added over 17 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 56 ° C. and ripened. After aging, 35μmol / g
Of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% was added. After adjusting the pH to 5.9, 2.9 g of KBr was added. A
288 ml of an aqueous solution containing 28.8 g of gNO ₃ and KBr
The aqueous solution was added by the double jet method over 53 minutes.
At this time, the AgI fine grain emulsion used in the preparation of Emulsion A-1 was simultaneously added so that the silver iodide content became 4.1 mol%, and the silver potential was adjusted to -60 with respect to the saturated calomel electrode.
mV. After adding 2.5 g of KBr, AgN
An aqueous solution containing 87.7 g of O ₃ and an aqueous KBr solution were added by a double jet method over a period of 63 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the AgI fine grain emulsion described above was mixed with a silver iodide content of 10.5 mol.
% At the same time and accelerated flow rate was added, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 m 2 of an aqueous solution containing 41.8 g of AgNO ₃ .
and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After adjusting the silver potential to -70 mV by adding KBr, the above AgI fine grain emulsion was converted to 5.7 in terms of KI weight.
3 g were added. Immediately after completion of the addition, AgNO ₃ , 66.
609 ml of an aqueous solution containing 4 g were added over 10 minutes. During the initial 6 minutes of the addition, the silver potential was lowered to -70 with an aqueous KBr solution.
mV. After washing with water, gelatin was added and the pH was adjusted to 6.5 and pAg at 8.2 at 40 ° C. Ag mentioned above
0.0004 mol of I fine grain emulsion per 1 mol of silver
After the addition, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate,
N, N- ヂ methylselenourea was added for optimal chemical sensitization. At the end of chemical sensitization, compounds 13 and 14 were added.

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(Preparation of Emulsion F) (Emulsion for Medium-Sensitive Green-Sensitive Layer) In the preparation of Em-E, the amount of AgNO ₃ added at the time of nucleation was changed to 3.1 times, and it was almost the same as Em-E. Prepared. However, the sensitizing dye of Em-E was replaced with sensitizing dyes 12,1.
Changed to 5, 16 and 17.

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(Preparation of Emulsion G) (Emulsion for low-sensitivity green-sensitive layer) Low-molecular weight gelatin having a molecular weight of 15,000 0.70 g, KB
r, 0.9 g, KI, 0.175 g, aqueous solution 1 containing modified silicone oil 0.2 g used in the preparation of emulsion A-1
200 ml was kept at 33 ° C., the pH was adjusted to 1.8, and the mixture was vigorously stirred. 2. an aqueous solution containing 1.8 g of AgNO ₃ and
An aqueous KBr solution containing 2 mol% of KI was added over 9 seconds by the double jet method. At this time, the excess concentration of KBr was kept constant. The temperature was raised to 69 ° C. to ripen. After completion of ripening, 27.8 g of trimellitated gelatin containing 35 μmol of methionine per gram and amino groups having a molecular weight of 100,000 and chemically modified with trimellitic acid was added.
After adjusting the pH to 6.3, 2.9 g of KBr was added. 270 ml of an aqueous solution containing 27.58 g of AgNO ₃
And an aqueous KBr solution were added by the double jet method over a period of 37 minutes. At this time, an aqueous solution of low molecular weight gelatin having a molecular weight of 15,000, an aqueous solution of AgNO _{3, and an} aqueous solution of KI were disclosed in
An AgI fine grain emulsion having a grain size of 0.008 μm prepared by mixing immediately before addition in a separate chamber having a magnetic coupling induction type stirrer described in No. 43570 so that the silver iodide content becomes 4.1 mol%. And the silver potential was kept at -60 mV with respect to the saturated calomel electrode. After adding 2.6 g of KBr, AgNO ₃ , 8
An aqueous solution containing 7.7 g and an aqueous KBr solution were added over 49 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 3.1 times the initial flow rate. At this time, the AgI fine grain emulsion prepared by mixing immediately before the above-described addition was simultaneously accelerated so that the silver iodide content became 7.9 mol%, and the silver potential was maintained at -70 mV. Thiourea dioxide, 1m
After adding g, 132 ml of an aqueous solution containing 41.8 g of AgNO3 and an aqueous KBr solution were added over 20 minutes by a double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After the temperature was raised to 78 ° C. and the pH was adjusted to 9.1, KBr was added to bring the potential to −60 mV. Ag used in the preparation of emulsion A-1
5.73 g of the I fine grain emulsion was added in terms of KI weight. Immediately after the addition was completed, 321 ml of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was maintained at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. Em-
Washed with water in almost the same manner as in F and chemically sensitized.

(Preparation of Emulsion H) (Emulsion for low-sensitive green-sensitive layer) Ion-exchanged gelatin having a molecular weight of 100,000 17.8.
g, KBr, 6.2 g, KI, 0.46 g in water at 45 ° C. and stirred vigorously. AgNO ₃ , 11.8
An aqueous solution containing 5 g and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After the temperature was raised to 63 ° C, ion-exchanged gelatin having a molecular weight of 100,000 2
4.1 g was added and ripened. After fully aged, AgN
An aqueous solution containing 133.4 g of O ₃ and an aqueous KBr solution were added over 20 minutes by a double jet method so that the final flow rate was 2.6 times the initial flow rate. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. Ten minutes after the start of the addition, 0.1 mg of K ₂ IrCl ₆ was added. N
After adding 7 g of aCl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by a double jet method. At this time, the silver potential was kept at +90 mV. 29 mg of yellow blood salt over 6 minutes from the start of addition
100 ml of an aqueous solution was added. 14.4 g of KBr
After the addition, 6.3 g of the AgI fine grain emulsion used in the preparation of Emulsion A-1 was added in terms of KI weight. After the addition,
Immediately, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water and chemically sensitized almost in the same manner as Em-F. (Preparation Method of Emulsion I) (Emulsion for Low-Sensitive Green-Sensitive Layer) Em-H was prepared in substantially the same manner as in Em-H except that the temperature during nucleation was changed to 38 ° C.

(Preparation Method of Emulsion J) (Emulsion for Highly Sensitive Red-Sensitive Layer) Phthalized gelatin having a phthalation ratio of 97% and a molecular weight of 100,000.
1200ml of aqueous solution containing 38g, KBr, 0.99g
Was maintained at 60 ° C., the pH was adjusted to 2, and the mixture was stirred vigorously. A
gNO ₃ , aqueous solution containing 1.96 g and KBr, 1.97
g, KI and an aqueous solution containing 0.172 g were added by the double jet method over 30 seconds. After ripening, molecular weight 10,000 containing 35 μmol methionine per 1 g
12.8 g of trimellitated gelatin obtained by chemically modifying amino group 0 with trimellitic acid was added. After adjusting the pH to 5.9, 2.99 g of KBr and 6.2 g of NaCl were added. An aqueous solution containing 27.3 g of AgNO ₃ 60.
7 ml and an aqueous KBr solution were added by the double jet method over 35 minutes. At this time, the silver potential was kept at -50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over a period of 37 minutes by a double jet method while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate. At this time, the AgI fine grain emulsion used in the preparation of Emulsion A-1 was adjusted to have a silver iodide content of 6.5 mol%.
At the same time, and the silver potential was maintained at -50 mV. After adding 1.5 mg of thiourea dioxide, an aqueous solution 132 containing 41.8 g of AgNO ₃ was added.
ml and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. The above AgI fine grain emulsion was added in an amount of 6.2 g in terms of KI weight. Immediately after the addition is completed, an aqueous solution 300 containing 88.5 g of AgNO _{3 is} added.
ml was added over 8 minutes. Potential at the end of addition is +6
It was adjusted to be 0 mV by adding an aqueous KBr solution. After washing with water, gelatin was added, and pH 6.5 and pA at 40 ° C.
g, adjusted to 8.2. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After addition of sensitizing dye 18, 19, 20 and 21, K ₂ IrCl _6, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-diethylene was optimally chemically sensitized by adding methyl seleno urea. At the end of chemical sensitization, compounds 13 and 14 were added.

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(Preparation of Emulsion K) (Emulsion for middle-sensitivity red-sensitive layer) 4.9 g of low molecular weight gelatin having a molecular weight of 15,000, KB
1200 ml of an aqueous solution containing 5.3 g of r was maintained at 60 ° C. and stirred vigorously. 27 ml of an aqueous solution containing 8.75 g of AgNO ₃ and 36 ml of an aqueous solution containing 6.45 g of KBr were added by a double jet method over 1 minute. After the temperature was raised to 77 ° C., 21 ml of an aqueous solution containing 6.9 g of AgNO ₃ .
Was added over 2.5 minutes. NH ₄ NO ₃ , 26 g,
After successively adding 56 ml of 1N and NaOH, the mixture was aged. After aging, the pH was adjusted to 4.8. AgNO ₃ ,
438 ml of an aqueous solution containing 141 g and 102.6 of KBr.
458 ml of an aqueous solution containing g was added by a double jet method so that the final flow rate was four times the initial flow rate. After cooling to 55 ° C., 240 ml of an aqueous solution containing 7.1 g of AgNO ₃
And an aqueous solution containing 6.46 g of KI by the double jet method.
Added over minutes. After adding 7.1 g of KBr, 4 mg of sodium benzenethiosulfonate and K ₂ IrC
l _6, was 0.05mg added. AgNO ₃ , 57.2 g
And 223 ml of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. It was washed with water and chemically sensitized almost in the same manner as Em-J. (Preparation of Emulsion L) (Emulsion for Medium-Sensitive Red-Sensitive Layer) Em-K was prepared in substantially the same manner as in Em-K except that the temperature during nucleation was changed to 42 ° C. (Preparation of Emulsions M, N, O) (Emulsion for low-sensitivity red-sensitive layer) The emulsion was prepared in substantially the same manner as Em-H or Em-I. However, the chemical sensitization was performed in substantially the same manner as in Em-J.

(Production method of emulsion P) (milk for high-sensitivity green-sensitive layer)
(Preparation of seed emulsion a) 0.017 g of KBr, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 60 ° C. and stirred. AgNO_Three (1.6
g) Aqueous solution, KBr aqueous solution and acid having an average molecular weight of 20,000
Triple jet of gelatinized aqueous solution (2.1g)
Was added over 30 seconds. At this time, the silver potential is
It was kept at 13 mV with respect to the Romel electrode. KBr aqueous solution
In addition, after setting the silver potential to −66 mV, the temperature was raised to 60 ° C.
Was. 21 g of succinated gelatin having an average molecular weight of 100,000
And then an aqueous solution of NaCl (5.1 g) was added.
Was. AgNO_Three (206.3g) Aqueous solution and KBr aqueous solution
For 61 minutes while accelerating the flow rate by the double jet method.
Was added. At this time, the silver potential is set with respect to the saturated calomel electrode.
And maintained at -44 mV. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
The pAg was adjusted to 8, and a seed emulsion was prepared. This species
The emulsion was 1 mol of Ag and 8 mol of gelatin per kg of emulsion.
Contains 0g, average equivalent circle diameter 1.46μm, equivalent circle diameter
Coefficient of variation 28%, average thickness 0.046 μm, average as
Tabular grains having a spect ratio of 45 were obtained. (Formation of core) 134 g of the above seed emulsion a, 1.9 KBr
g, 22 g of succinated gelatin having an average molecular weight of 100,000
1200 ml of an aqueous solution containing was stirred at 75 ° C. A
gNO _Three (43.9 g) aqueous solution, KBr aqueous solution and molecular weight
A 20,000 gelatin aqueous solution was prepared as described in JP-A-10-43570.
Having a magnetic coupling induction stirrer as described in
Mix just before addition in chamber and add over 25 minutes
did. At this time, the silver potential was -4 with respect to the saturated calomel electrode.
It was kept at 0 mV. (Formation of First Shell) After the formation of the core particles, AgNO
_Three (43.9 g) aqueous solution, KBr aqueous solution and molecular weight 200
Add 00 aqueous gelatin solution in another chamber as above
Mix immediately before and after and add over 20 minutes. At this time, silver
The potential was kept at -40 mV with respect to the saturated calomel electrode. (Formation of Second Shell) After the formation of the first shell, AgN
O_Three (42.6 g) aqueous solution, KBr aqueous solution and molecular weight 20
000 gelatin solution in another chamber as above
The mixture was mixed just before addition and added over 17 minutes. At this time,
Keep the silver potential at -20 mV with respect to the saturated calomel electrode.
Was. Thereafter, the temperature was lowered to 55 ° C. (Formation of Third Shell) After the formation of the second shell, the silver potential
Is adjusted to -55 mV, and AgNO_Three (7.1 g) aqueous solution
And KI (6.9 g) aqueous solution and gelatin of 20,000 molecular weight
The aqueous solution is mixed immediately before addition in another chamber
Over 5 minutes. (Formation of Fourth Shell) After the formation of the third shell, AgN
O_Three (66.4 g) aqueous solution and KBr aqueous solution
The solution was added at a constant flow rate over a period of 30 minutes by a wet method. In the middle
Iridium potassium hexachloride and yellow blood salt were added. this
The silver potential at 30 mV relative to the saturated calomel electrode.
Was. Perform normal water washing, add gelatin, and add
H5.8 and pAg8.8 were adjusted. Emulsion b
And Emulsion b had an average equivalent circle diameter of 3.3 μm and an equivalent circle diameter.
Coefficient of variation 21%, average thickness 0.090 μm, average aspect ratio
These were tabular grains having an aspect ratio of 37. Also, 7 of the total projected area
0% or more has a circle equivalent diameter of 3.3μ or more and a thickness of 0.090μ or more
Occupied by lower tabular grains. Gain in this way
Table 2 shows the characteristics of the obtained silver halide emulsions A to P.

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[Table 2]

1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P. as an ultraviolet absorber. Three
26 (manufactured by Ciba-Geigy) and 2 parts by weight were dried, melted at 300 ° C., extruded from a T-die, and stretched longitudinally 3.3 times at 140 ° C., followed by 130 ° C. The film is stretched 3.3 times in the direction of
For 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye and a yellow dye (public technique: I-1 described in Japanese Patent Publication No. 94-6023,
I-4, I-6, I-24, I-26, I-27, II-
5) was added in an appropriate amount. Further, the support was wound around a stainless steel winding core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled. 2) Coating of Undercoat Layer The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α-sulfodi-2 were applied to each surface. −
Ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g
/ M ² , (CH ₂ ＣＨCHSO ₂ CH ₂ CH ₂ NHCO)
₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat solution is applied (10 cc / m ² , using a bar coater), and the undercoat layer is placed on the high temperature side during stretching. Provided. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat. 3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm which is a dispersion of fine particle powder (secondary aggregated particle size of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH
₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.00
Coated with 5 g / m ² and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ²⁺ / Fe ³⁺ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m2 Diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand mill), as a curing agent _{C 2 H 5 C (CH 2} OCONH-C 6
0.3 g / m ² of H ₃ (CH ₃ ) NCO) ₃ was applied by a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. Silica particles (0.3 μm) and 3 as matting agent
10 mg each of an abrasive aluminum oxide (0.15 μm) coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight)
/ M ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 11
5 ° C). The X-light (blue filter) increases the color density of DB of the magnetic recording layer by about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.
3 × 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ C
H (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg
/ M ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. Note that this mixture is composed of xylene / propylene monomethyl ether (1
/ 1) was melted at 105 ° C. and poured into and dispersed in propylene monomethyl ether (10-fold amount) at room temperature to prepare
The dispersion was added in acetone (average particle size: 0.01 μm) and then added. Silica particles (0.3μm) as matting agent
And 15 mg / aluminum oxide (0.15 μm) each coated with 3-poly (degree of polymerization 15) oxyethylenepropyloxytrimethoxysilane (15% by weight) as an abrasive.
m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.)
° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless steel hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of 0.12 between the emulsion surface and the sliding layer described later. Excellent characteristics.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, layers having the following compositions were applied in a multi-layered manner.
01 to 104 were created. That is, samples 101 to 104 were prepared by replacing silver iodobromide emulsion A-1 in the fourteenth layer with emulsions A-2 to A-4, respectively. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener (Specific compounds are described below, numbers are added after symbols, and chemical formulas are listed after the numbers.) The number corresponding to each component is the coating amount in g / m ^2. And for silver halide, the coating amount in terms of silver is shown. First layer (first antihalation layer) Black colloidal silver silver 0.155 0.07μ surface fogging AgBrI (2) silver 0.01 gelatin 0.87 ExC-1 0.002 ExC-3 0.002 Cpd- 2 0.001 HBS-1 0.004 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.066 Gelatin 0.407 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.015 Solid disperse dye ExF-3 0.020 Third layer (intermediate layer) 0.07 μg AgBrI (2) 0.020 ExC-2 022 polyethyl acrylate latex 0.085 gelatin 0.294 fourth layer (low-sensitivity red-sensitive emulsion layer) silver iodobromide emulsion M silver 0.065 silver iodobromide emulsion N silver 100 silver iodobromide emulsion O silver 0.158 ExC-1 0.109 ExC-3 0.044 ExC-4 0.072 ExC-5 0.011 ExC-6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.80 Fifth layer (Medium sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion K silver 0.21 Silver iodobromide emulsion L silver 0.62 ExC-1 0.14 ExC-2 0.026 ExC-3 0.020 ExC-4 0.12 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1 .18 6th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion J silver 1.67 ExC-1 0.18 ExC-3 0.07 ExC-6 0.029 ExC-7 0.010 ExY-5 0.008 Cpd- 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12 7th layer (middle layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.84 Eighth layer (multilayer effect donor layer (layer giving multilayer effect to red-sensitive layer)) Silver iodobromide emulsion E silver 0.560 Cpd-4 0.030 ExM-2 0.096 ExM-3 0.028 ExY-1 0.031 ExG-1 0.006 HBS-1 0.085 HBS-3 0.003 Gelatin 0.58 9th layer (low-sensitivity green-sensitive emulsion layer) ) Silver iodobromide emulsion G silver 0.39 silver iodobromide emulsion H silver 0.28 silver iodobromide emulsion I silver 0.35 ExM-2 0.36 ExM-3 0.045 ExG-1 0.005 HBS 1 0.28 HBS-3 0.01 HSB-4 0.27 Gelatin 1.39 10th layer (Medium speed green-sensitive emulsion layer) Silver iodobromide emulsion F silver 0.20 Silver iodobromide emulsion G silver 25 ExC-6 0.009 ExM-2 0.031 ExM-3 0.029 ExY-1 0.006 ExM-4 0.028 ExG-1 0.005 HBS-1 0.064 HBS-3 2.1 × 10 ^-3 gelatin 0.44 Eleventh layer (high-sensitivity green-sensitive emulsion layer) Emulsion P of Example-2 Silver 1.200 ExC-6 0.004 ExM-1 0.016 ExM-3 0.036 ExM-4 0.020 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 ExG-1 0.005 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 Gelatin 1 11 12th layer (yellow filter layer) yellow colloidal silver silver 0.047 Cpd-1 0.16 solid disperse dye ExF-5 0.010 solid disperse dye ExF-6 0.010 HBS-1 0.082 gelatin 1.057 13th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion B silver 0.18 silver iodobromide emulsion C silver 0.20 silver iodobromide emulsion D silver 0.07 ExC-1 0.041 ExC-8 0.012 ExY-1 0.035 ExY-2 0.71 ExY-3 0.10 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A-1 Silver 0.75 ExC-1 0.013 ExY-2 0.31 ExY-3 0.05 ExY-6 0.062 Cpd-2 0.075 ^{pd-3 1.0 × 10 -3 HBS} -1 0.10 Gelatin 0.91 15th layer (first protective layer) 0.07 of AgBrI (2) silver 0.30 UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-18 0.009 F-19 0.005 F-20 0.005 HBS-1 0.12 HBS-4 5.0 × 10 ^-2 gelatin 2.3 Sixteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-30 .05 S-1 0.20 Gelatin 0.75 Further, each layer may have a preservability, a processing property, a pressure resistance, an antifungal property.
Contains antibacterial properties, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, ruthenium salts, and rhodium salts.
In addition, the coating liquid for the eighth layer was added in an amount of 8.8 per mol of silver halide.
A sample was prepared by adding 5 × 10 ⁻³ g of calcium and 7.9 × 10 ⁻³ g of calcium to the eleventh layer with an aqueous solution of calcium nitrate. In order to further improve the antistatic property, W-1 and W-
6, W-7 and W-8, and at least one of W-2 and W-5 to improve coating properties. Preparation of Dispersion of Organic Solid Disperse Dye ExF-3 below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were put into a 700 ml pot mill. , Dye ExF-
5.0 g and zirconium oxide beads (diameter 1 mm)
500 ml was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles is 0.4
It was 4 μm. Similarly, a solid dispersion of ExF-4 was obtained. The average particle diameter of the fine dye particles is 0.24 μ, respectively.
m, 0.45 μm, and 0.52 μm. ExF-2
Are described in Example 1 of EP-A-549,489A.
pitition). The average particle size was 0.06 μm. The solid dispersion of ExF-6 was dispersed by the following method. To 2800 g of ExF-6 wet cake containing 18% of water, 4000 g of water and 3 of W-2 were added.
376 g of the ExF-6% solution was added and stirred.
% Slurry. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec and the discharge rate was 0.5 liter / mi.
n for 8 hours. The compounds used to form the above layers are as shown below.

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[0320]

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The evaluation method of the sample is as follows. Exposure was performed for 1/100 second through a continuous wedge and a gelatin filter SC-39 (a long wavelength light transmission filter having a cutoff wavelength of 390 nm) manufactured by FUJIFILM Corporation. The development was performed as follows using an automatic developing machine FP-360B manufactured by Fuji Photo Film Co., Ltd. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank.
This FP-360B is disclosed by the Japan Institute of Invention and Innovation 94-4992
The evaporation correction means described in the above item. The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 ml 11.5 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liters Fixing (1) 50 seconds 38.0 ° C ─ 5 liters Fixing (2 ) 50 seconds 38.0 ℃ 8 ml 5 liters Rinse 30 seconds 38.0 ℃ 17 ml 3 liters stable (1) 20 seconds 38.0 ℃ ─ 3 liters stable (2) 20 seconds 38.0 ℃ 15 ml 3 liters drying 1 minute 30 seconds 60.0 ℃ * The replenishment amount is 35 m of photosensitive material per 1.1 m width (corresponding to 24 Ex. 1 bottle). The stabilizer and the fixer are countercurrent systems from (2) to (1). 2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 35 m width of the photosensitive material and 1.1 m. Milliliters and 2.0 milliliters. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 c for color developer.
m ² , 120cm ^{2 for} bleaching solution, about 10 other processing solutions
It was 0 cm ² . The composition of the treatment liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy-6 Methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate Salt 4.5 6.5 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18 (bleach) Tank liquid (g Replenisher (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Add water 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0 (Fixing (1) tank solution) A mixture of the above bleaching tank solution and the following fixing tank solution in a ratio of 5:95 (volume ratio).

(PH 6.8) (Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 ml 720 ml (750 g / l) imidazole 721 ammonium methanethiosulfonate 515 ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 L 1.0 L pH [adjusted with ammonia water and acetic acid] 7.4 7.45 (Washing water) Tap water is replaced with H-type strongly acidic cation exchange resin (ROHM) Amberlite IR-120B manufactured by Andhas)
And through a mixed-bed column filled with an OH-type strongly basic anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by isocyanuric dichloride 20 mg / liter of sodium acid and 150 mg /
One liter was added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-Benzoisothiazoline-3 -One sodium 0.10 disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 water In addition, 1.0 liter pH 8.5

Measurement of the light absorption intensity per unit area was performed in the same manner as in Example 1. The results are shown in Table 3.

[0324]

[Table 3]

In the table, the light absorption intensity, 50% interval of Amax, and the ratio of the particles having the absorption maximum wavelength in the wavelength range of 10 nm are the values obtained by measuring the emulsions A-1 to A-4 by microspectroscopy. Indicated. The sensitivities and gradations were determined by measuring the yellow color densities of the samples 101 to 104. According to the present invention, it has been clarified that the sensitizing dye adsorption state can be made uniform among the particles, and that the high sensitivity can be further enhanced as compared with the conventional multilayer adsorption system.

[0326]

From the examples of the present invention, it is possible to obtain a silver halide photographic light-sensitive material having a high sensitivity and a small distribution of particles in the dye-adsorbed state even in an emulsion in which sensitizing dyes are adsorbed in multiple layers according to the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/02 G03C 5/02 7/00 510 7/00 510

Claims (17)

[Claims] 2. The method according to claim 1, wherein the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the spectral absorption maximum wavelength is 500.
A silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 100 nm or more and having a light absorption intensity of 100 or more, wherein the coefficient of variation of the distribution of light absorption intensity between the grains is 100% or less. . 2. The spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the spectral absorption maximum wavelength is 500
In a silver halide photographic emulsion containing silver halide grains having a light absorption intensity of not less than 100 nm and a light absorption intensity of not less than 100, the maximum value of the spectral absorption by the sensitizing dye is defined as Amax.
%. The silver halide photographic emulsion characterized in that the coefficient of variation of the intergranular distribution of the wavelength interval between the shortest wavelength and the longest wavelength indicates 50% or less. 3. The light having a maximum spectral absorption wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a maximum spectral absorption wavelength of 500.
In a silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 100 nm or more and having a light absorption intensity of 100 nm or more, the spectral absorption maximum wavelength of the grains having 50% or more of the total projected area is within a range of 10 nm or less. Silver halide emulsion. 4. The silver halide photographic emulsion according to claim 1, comprising a silver halide photographic emulsion in which a sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grains. 5. The silver halide photographic emulsion according to claim 4, wherein the interaction energy between the first-layer dye and the second-layer dye is 10% or more of the total adsorption energy of the second-layer dye. The silver halide photographic emulsion according to claim 4. 6. The silver halide photographic emulsion according to claim 1, wherein the maximum value of the spectral absorptivity of said emulsion by a sensitizing dye is Amax, and the shortest wavelength and 50% of Amax are the same. The silver halide photographic emulsion according to any one of claims 1 to 5, wherein a long wavelength interval is 120 nm or less. 7. The silver halide photographic emulsion according to claim 1, wherein, when the maximum value of the spectral sensitivity of the emulsion by a sensitizing dye is Smax, the shortest wavelength and the longest wavelength exhibit 50% of Smax. 6. The silver halide photographic emulsion according to claim 1, wherein a wavelength interval of the wavelength is 120 nm or less. 8. The silver halide photographic emulsion according to claim 6, wherein the longest wavelength having a spectral absorption of 50% of Amax is from 460 nm to 510 nm or 560 nm.
The silver halide photographic emulsion according to claim 6 or 7, wherein the thickness is in the range of from 610 nm to 610 nm or from 640 nm to 730 nm. 9. The silver halide photographic emulsion according to claim 6, wherein the longest wavelength showing a spectral sensitivity of 50% of Smax is in the range of 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm. The silver halide photographic emulsion according to claim 6 or 7, wherein 10. The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion contains a dye having at least one aromatic group. 11. The silver halide photographic emulsion according to claim 1, further comprising a sensitizing dye having a basic nucleus fused with three or more rings. 12. The silver halide photographic emulsion according to claim 1, wherein tabular grains having an aspect ratio of 2 or more are present in an amount of 50% or more (area) of all silver halide grains in the emulsion. The silver halide photographic emulsion according to any one of claims 1 to 11, wherein 13. The silver halide photographic emulsion according to claim 1, wherein the silver halide photographic emulsion according to claim 1 is sensitized with selenium. 14. The silver halide photographic emulsion according to claim 1, further comprising a silver halide-adsorbing compound other than a sensitizing dye. Silver halide photographic emulsion. 15. The silver halide grains of the silver halide photographic emulsion according to claim 1, wherein the excitation energy of the second-layer dye is transferred to the first-layer dye at an efficiency of 10% or more. The silver halide photographic emulsion according to any one of claims 1 to 14, wherein 16. The silver halide grains of the silver halide photographic emulsion according to claim 1, wherein both the first-layer dye and the second-layer dye exhibit J-band absorption. A photographic silver halide emulsion according to any one of the above. 17. A silver halide photographic material comprising at least one silver halide photographic emulsion according to claim 1. Description: